Cleaning implement with a rheological solid composition

ABSTRACT

A cleaning implement for cleaning a target surface is provided that includes an erodible foam adapted to contact a surface to be cleaned and a rheological solid composition comprising a crystallizing agent and an aqueous phase.

FIELD OF THE INVENTION

The invention relates to a cleaning implement comprising erodible foamthat is adapted to contact a surface to be cleaned and a rheologicalsolid composition comprising more than about 80% water having acrystallizing agent with an elongated, fiber-like crystal habit. Whereinthe rheological solid composition allows for a unique aqueous phaseexpression when rubbed on a hard surface.

BACKGROUND OF THE INVENTION

Use of an erodible foam, such as melamine-formaldehyde resin foam(“melamine foam”) for hard surface cleaning is well known. Cleaningimplements of cut or molded melamine foam are popular for removing soilsand stains from hard surfaces. Melamine foams are currently marketed insome countries under the tradename of Mr. Clean Magic Eraser™. Melaminefoams, when wetted with an appropriate solvent, show excellent soil andstain removal in cleaning hard surfaces. Although melamine foam isgenerally effective in removing soils and stains from hard surfaces,consumers may find it difficult to remove certain kinds of tough stainswith melamine foam, even after applying extra rubbing force.

To improve the cleaning performance of melamine foam over tough stains,one may use a detergent composition along with the melamine foam toclean. The sponge and detergent can be provided separately or the spongemay be impregnated with the detergent. Consumers may still find itinconvenient to apply the detergent and then scrub. Further, spongesimpregnated with detergents tend to release the active agents quickly,leading to significant loss of the active agent after the first severaluses. In turn, reduced cleaning properties are observed as the activeagent is used up. Also, when an active agent releases quickly in thefirst or second use, the high level of active agent may require extrarinsing.

Conventional high-water containing compositions, such as rheologicalsolid compositions, lack one or more desirable properties, forexample—sufficient firmness, aqueous phase expression and thermalstability, particularly those comprising sodium carboxylate-basedcrystallizing agents. For instance, to produce a firm rheological solidcomposition using sodium stearate (C18) as a gelling agent inconventional soap-type deodorant gel-sticks requires the inclusion ofhigh levels of polyols (e.g. propylene glycol and glycerin), as asolubility aid for the sodium stearate during processing, even at highprocess temperatures. Typical compositions include about 50% propyleneglycol, 25% glycerin and only 25% water (EP2170257 and EP2465487).However, the addition of these processing aids eliminates the crunch andmutes the glide feel and cooling sensation of the solid gel stick. For asecond example, traditional soap bars are comprised of similar gellingagents, but are far too concentrated in sodium carboxylate toeffectively allow for aqueous phase expression with compression. Anotherexample is where thermal stability is compromised in compositions byadding a too soluble gelling agent, as in (Kacher et al., U.S. Pat. No.5,340,492). Specifically, the thermal stability temperature of thecomposition is too low to effectively survive reliably on the shelf lifeor in the supply chain.

What is needed is a cleaning implement that includes a rheological solidcomposition that has sufficient firmness, an improved aqueous phaseexpression and thermal stability. The present invention of aself-supporting structure comprising a crystalline mesh of a relativelyrigid, frame of fiber-like crystalline particles, which if compressedexpresses aqueous phase provides the properties of sufficient firmness,thermal stability, and aqueous phase expression.

SUMMARY OF THE INVENTION

A cleaning implement including an erodible foam adapted to contact asurface to be cleaned and a rheological solid composition is providedthat comprises crystallizing agent and aqueous phase; wherein, therheological solid composition has a firmness between about 0.1 N toabout 50.0 N as determined by the FIRMNESS TEST METHOD; a thermalstability of about 40° C. to about 95° C. as determined by the THERMALSTABILITY TEST METHOD; a liquid expression of between about 100 J m-3 toabout 8,000 J m-3 as determined by the AQUEOUS PHASE EXPRESSION TESTMETHOD; and wherein the crystallizing agent is a salt of fatty acidscontaining from about 13 to about 20 carbon atoms.

BRIEF DESCRIPTION OF THE DRAWINGS

While the specification concludes with claims particularly pointing outand distinctly claiming the subject matter that is regarded as thepresent disclosure, it is believed that the disclosure will be morefully understood from the following description taken in conjunctionwith the accompanying drawings. Some of the figures may have beensimplified by the omission of selected elements for the purpose of moreclearly showing other elements. Such omissions of elements in somefigures are not necessarily indicative of the presence or absence ofparticular elements in any of the exemplary embodiments, except as maybe explicitly delineated in the corresponding written description. Noneof the drawings are necessarily to scale.

FIG. 1. X-ray Diffraction Pattern

FIG. 2. SEM of Interlocking Mesh

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a cleaning implement that includes anerodible foam adapted to contact a surface to be cleaned and alsoincludes a rheological solid composition comprising a crystalline mesh.The crystalline mesh (“mesh”) comprises a relatively rigid,three-dimensional, interlocking crystalline skeleton frame of fiber-likecrystalline particles (formed from crystallizing agents), having voidsor openings containing aqueous solution and optionally one or moreactives. The mesh provides a self-supporting structure, such that arheological solid composition may ‘stand on its own’ when resting on asurface. If compressed above a critical stress, the mesh allows therheological solid composition to express the entrapped aqueous phase,and optionally water soluble actives. The rheological solid compositionsof the present invention include crystallizing agent(s), aqueous phaseand optionally active and may be combined with a device to enableapplication.

It is surprising that it is possible to prepare rheological solidcompositions that exhibit sufficient firmness, aqueous phase expressionand thermal stability. Not wishing to be bound by theory, it is believedthat sodium carboxylates present in high-water compositions (e.g. aboveabout 80%) and correct chain length purity may form elongated,fiber-like crystal habits. These crystals form mesh structures thatresult in rheological solid compositions even at very lowconcentrations. Firmness may be achieved by carefully adjusting theconcentration and chain length distribution of the crystallizing agent.Aqueous phase expression may be achieved from these rheological solidstructures, by compression above ayield behavior that breaks the meshstructure allowing the water to flow from the composition. One skilledin the art recognizes this as a plastic deformation of the meshstructure. This stands in contrast to other gelling agents like gelatin,that can be formulated at very high-water concentrations but do notexpress water with compression. Thermal Stability may be achieved byensuring the proper chain length and chain length distributions toensure the mesh does not solubilize when heated above 40° C. This is animportant property in relation to the shelf-life and supply chain forconsumer products. Addition of sodium chloride can be used to increasethe thermal stability of the composition but should be added correctlyto ensure the proper formation of the mesh. These discovered designelements stand in contrast to compositions prepared with too-soluble agelling agent to be practically thermal stable. Finally, suchrheological solid compositions are prepared by cooling the mixturelargely quiescently, in contrast to freezer or other mechanicallyinvasive processes. Not wishing to be bound by theory, quiescentprocesses allow the formation of very large and efficient fibrouscrystals rather the breaking them into smaller less efficient crystals.

Erodible Foam

The erodible foam herein is an article of manufacture of any suitableshape, size, and/or volume suitable for removing spots and/or stainsfrom surfaces. The erodible foam substrate, in one embodiment, is aheat-compressed erodible foam substrate. By “heat-compressed”, it ismeant that the erodible foam has been subject to two distinctoperations: a heating step and a compression step. “Erodible foam”herein means foam which crumbles into small particles and peels off byfriction. Suitable erodible foam includes, but is not limited to,melamine foam, phenolic foam, etc. According to one embodiment of thepresent invention, the erodible foam is a heat-compressed melamine.

Principles for manufacturing melamine-based foams and compressedmelamine-based foams are well known. Melamine-based foams are currentlymanufactured by BASF (Ludwigshafen, Germany) under the BASOTECT® brandname. For example, BASOTECT® 2011, with a density of about 0.01 g/cm3,may be used. Blocks of melamine-based foam for cleaning are marketed byProcter & Gamble (Cincinnati, Ohio) under the MR. CLEAN® brand name, andunder the CLEENPRO™ name by LEC, Inc. of Tokyo, Japan (several productexecutions are shown athttp://www.users.bigpond.com/jmc.au/CLEENPRO/CLEENPRO-E.htm andhttp://www.users.bigpond.com/jmc.au/CLEENPRO/CLEENPRO%20Family-E.htm,both printed on Nov. 13, 2003). Melamine-based foam is also marketed foracoustic and thermal insulation by many companies such as American MicroIndustries (Chambersburg, Pa.).

Principles for production of melamine-based foam are also disclosed byH. Mahnke et al. in EP-B 071 671, published Dec. 17, 1979. According toEP-B 017 671, they are produced by foaming an aqueous solution ordispersion of a melamine-formaldehyde condensation product whichcomprises an emulsifier (e.g., metal alkyl sulfonates and metalalkylaryl sulfonates such as sodium dodecylbenzene sulfonate), an acidiccuring agent, and a blowing agent, such as a C5-C7 hydrocarbon, andcuring the melamine-formaldehyde condensate at an elevated temperature.The foams are reported to have the following range of properties:

a density according to DIN 53 420 between 4 and 80 grams per liter(g/l), corresponding to a range of 0.004 g/cc to 0.08 g/cc (though forpurposes of the present invention the density can also range from about0.006 g/cc to about 0.1 g/cc, or other useful ranges);

a thermal conductivity according to DIN 52 612 smaller than 0.06 W/m °K;

a compression hardness according to DIN 53 577 under 60% penetration,divided by the density, yielding a quotient less than 0.3 (N/cm2)/(g/l),and preferably less than 0.2 (N/cm2)/(g/l), whereby after measurement ofcompression hardness the thickness of the foam recovers to at least 70%and preferably at least 90% of its original thickness;

an elasticity modulus according to DIN 53 423, divided by the density ofthe foam, under 0.25 (N/mm2)/(g/l) and preferably under 0.15(N/mm2)/(g/l);

a bending path at rupture according to DIN 53 423 greater than 6 mm andpreferably greater than 12 mm; and

a tensile strength according to DIN 53 571 of at least 0.07 N/mm2 orpreferably at least 0.1 N/mm2.

The foam may be molded or shaped into three-dimensional shapes foraesthetic or functional purposes. For example, melamine-based foam maybe thermally molded according to the process disclosed in U.S. Pat. No.6,608,118, “Melamine Molded Foam, Process for Producing the Same, andWiper,” issued Aug. 19, 2003 to Y. Kosaka et al., herein incorporated byreference, which discloses molding the foam at 210 to 350 C (or, moreparticularly, from 230° C. to 280° C. or from 240° C. to 270° C.) for 3minutes or longer to cause plastic deformation under load, wherein thefoam is compressed to a thickness of about 1/1.2 to about 1/12 theoriginal thickness, or from about 1/1.5 to about 1/7 of the originalthickness.

As described by Kosaka et al., the melamine-based foam can be producedby blending major starting materials of melamine and formaldehyde, or aprecursor thereof, with a blowing agent, a catalyst and an emulsifier,injecting the resultant mixture into a mold, and applying or generatingheat (e.g., by irradiation or electromagnetic energy) to cause foamingand curing. The molar ratio of melamine to formaldehyde (i.e.,melamine:formaldehyde) for producing the precursor is said to be 1:1.5to 1:4, or more particularly 1:2 to 1:3.5. The number average molecularweight of the precursor can be from about 200 to about 1,000, or fromabout 200 to about 400. Formalin, an aqueous solution of formaldehyde,can be used as a formaldehyde source.

As monomers for producing the precursor, according to Kosaka et al., thefollowing monomers may be used in an amount of 50 parts by weight(hereinafter abbreviated as “parts”) or less, particularly 20 parts byweight or less, per 100 parts by weight of the sum of melamine andformaldehyde. Melamine is also known by the chemical name2,4,6-triamino-1,3,5-triazine. As other monomers corresponding tomelamine, there may be used C1-5 alkyl-substituted melamines such asmethylolmelamine, methylmethylolmelamine and methylbutylolmelamine,urea, urethane, carbonic acid amides, dicyandiamide, guanidine,sulfurylamides, sulfonic acid amides, aliphatic amines, phenols and thederivatives thereof. As aldehydes, there may be used acetaldehyde,trimethylol acetaldehyde, acrolein, benzaldehyde, furfurol, glyoxal,phthalaldehyde, terephthalaldehyde, and the like.

As the blowing agent, there may be used pentane, trichlorofluoromethane,trichlorotrifluoroethane, etc. As the catalyst, by way of example,formic acid may be used and, as the emulsifier, anionic surfactants suchas sodium sulfonate may be used.

The amount of the electromagnetic energy to be irradiated foraccelerating the curing reaction of the reaction mixtures can beadjusted to be from about 500 to about 1,000 kW, or from about 600 to800 kW, in electric power consumption based on 1 kg of an aqueousformaldehyde solution charged in the mold. If the electric power appliedis insufficient, there may be insufficient foaming, leading toproduction of a cured product with a high density. On the other hand, incase when the electric power consumption is excessive, the pressure uponfoaming becomes high, leading to significant exhaust flows from the moldand even the possibility of explosion.

Other useful methods for producing melamine-based foam are disclosed inU.S. Pat. No. 5,413,853, “Melamine Resin Foam,” issued May 9, 1995 to Y.Imashiro et al., herein incorporated by reference. According to Imashiroet al., a melamine resin foam can be obtained by coating a hydrophobiccomponent on a known melamine-formaldehyde resin foam body obtained byfoaming a resin composition composed mainly of a melamine-formaldehydecondensate and a blowing agent. The components used in the presentmelamine resin foam can therefore be the same as those conventionallyused in production of melamine-formaldehyde resins or their foams,except for the hydrophobic component.

As an example, Imashiro et al. disclose a melamine-formaldehydecondensate obtained by mixing melamine, formalin and paraformaldehydeand reacting them in the presence of an alkali catalyst with heating.The mixing ratio of melamine and formaldehyde can be, for example, 1:3in terms of molar ratio.

The melamine-formaldehyde condensate can have a viscosity of about1,000-100,000 cP, more specifically 5,000-15,000 cP and can have a pH of8-9.

As the blowing agent, a straight-chain alkyl hydrocarbon such as pentaneor hexane is disclosed.

In order to obtain a homogeneous foam, the resin composition composedmainly of a melamine-formaldehyde condensate and a blowing agent maycontain an emulsifier. Such an emulsifier includes, for example, metalalkylsulfonates and metal alkylarylsulfonates.

The resin composition may further contain a curing agent in order tocure the foamed resin composition. Such a curing agent includes, forexample, acidic curing agents such as formic acid, hydrochloric acid,sulfuric acid and oxalic acid.

The foam disclosed by Imashiro et al. can be obtained by adding asnecessary an emulsifier, a curing agent and further a filler, etc. tothe resin composition composed mainly of a melamine-formaldehydecondensate and a blowing agent, heat-treating the resulting mixture at atemperature equal to or higher than the boiling point of the blowingagent to give rise to foaming, and curing the resulting foam.

In another embodiment, the foam material may comprise a melamine-basedfoam having an isocyanate component (isocyanate-based polymers aregenerally understood to include polyurethanes, polyureas,polyisocyanurates and mixtures thereof). Such foams can be madeaccording to U.S. Pat. No. 5,436,278, “Melamine Resin Foam, Process forProduction Thereof and Melamine/Formaldehyde Condensate,” issued Jul.25, 1995 to Imashiro et al., herein incorporated by reference, whichdiscloses a process for producing a melamine resin foam comprising amelamine/formaldehyde condensate, a blowing agent and an isocyanate. Oneembodiment includes the production of a melamine resin foam obtained byreacting melamine and formaldehyde in the presence of a silane couplingagent. The isocyanate used in U.S. Pat. No. 5,436,278 can be exemplifiedby CR 200 (a trademark of polymeric-4,4′-diphenylmethanediisocyanate,produced by Mitsui Toatsu Chemicals, Inc.) and Sumidur E211, E212 and L(trademarks of MDI type prepolymers, produced by Sumitomo Bayer UrethaneCo., Ltd). One example therein comprises 100 parts by weight ofmelamine/formaldehyde condensate (76% concentration), 6.3 parts sodiumdodecylbenzenesulfonate (30% concentration), 7.6 parts pentane, 9.5parts ammonium chloride, 2.7 parts formic acid, and 7.6 parts CR 200. Amixture of these components is placed in a mold and foamed at 100° C.,yielding a material with a density of 26.8 kg/m3 (0.0268 g/cm3), acompression stress of 0.23 kgf/cm2, and a compression strain of 2.7%. Ingeneral, the melamine-based foams of U.S. Pat. No. 5,436,278 typicallyhave a density of 25-100 kg/m3, a compression strain by JIS K 7220 of2.7%-4.2% (this is said to be improved by about 40%-130% over the 1.9%value of conventional fragile melamine foams), and a thermalconductivity measured between 10° C. to 55° C. of 0.005 kcal/m-h-° C. orless (this is far smaller than 0.01 kcal/m-h-° C. which is said to bethe value of conventional fragile foam). Other foams comprising melamineand isocyanates are disclosed in WO 99/23160, “Composition and Methodfor Insulating Foam,” published May 14, 1999 by Sufi, the U.S.equivalent (application U.S. Pat. No. 9,823,864) is herein incorporatedby reference.

Suitable shapes of the erodible foam herein may be selected from thegroup consisting of a cubic shape, a rectangular shape, a pyramidalshape, a cylindrical shape, a conical shape, an oblique rectangularprism shape, a cuboid shape, a tetrahedron shape, a sphere shape, aglobular shape, and an ellipsoid shape. “Oblique rectangular prismshape” herein means a voluminous body having six walls, wherein threepairs of parallel and equally shaped and sized walls exist and whereinone pair of walls are in the shape of a parallelogram and the remainingtwo pairs of walls are of rectangular shape.

Crystallizing Agent(s)

In the present invention the mesh of a rheological solid compositionincludes fiber-like crystalline particles formed from crystallizingagents; wherein “crystallizing agent” as used herein includes sodiumsalts of fatty acid with shorter chain length (C13-C20), such as sodiumpalmitate (C16). Commercial sources of crystallizing agent usuallycomprise complicated mixtures of molecules, often with chain lengthsbetween C10 to C22. The rheological solid compositions are best achievedwith a ‘narrow blend’- or distribution of crystallizing agent chainlengths, further best achieved with blends in the absence of very shortchain lengths (C12 or shorter) and measurable amounts of unsaturation onthe chains of the fatty acid sodium salts, and best achieved with asingle chain length between C13 to C20, coupled with controlledcrystallizing processing. Accordingly, rheological solid compositionsare best achieved when the blend of the chain length distribution ispreferably greater than about Po>0.3, more preferably about Po>0.5, morepreferably about Po>0.6, more preferably about Po>0.7 and mostpreferably about Po>0.8,_as determined by the BLEND TEST METHOD. Oneskilled in the art, recognizes crystalline particles as exhibiting sharpscattering peaks between 0.25-60 deg. 20 in powdered x-ray diffractionmeasurements. This is in sharp contrast to compositions in which thesematerials are used as gelling agents, which show broad amorphicscattering peaks emanating from poorly formed solids which lack thelong-range order of crystalline solids (FIG. 1).

Rheological solid compositions comprise greater than about 80% water andare ‘structured’ by a mesh of interlocking, fiber-like crystallineparticles of mostly single-chain length, as described above, see (FIG.2). The term ‘fiber-like crystalline particle’ refers to a particle inwhich the length of the particle in the direction of its longest axis isgreater than 10× the length of the particle in any orthogonal direction.The fiber-like crystalline particles produce a mesh at very lowconcentrations (˜0.5 wt %) which creates a solid that yields only with aminimum applied stress—i.e. rheological solid. The aqueous phaseprimarily resides in the open spaces of the mesh. In preparing thesecompositions, the crystallizing agent is dissolved in aqueous phaseusing heat. The fiber-like crystalline particles form into the mesh asthe mixture cools over minutes to hours.

Such compositions exhibit three properties used to make effectiveconsumer product for envisioned applications:

Aqueous Phase Expression

Aqueous phase expression is an important property for consumerapplications in the present invention, expressed in work to expresswater per unit volume, where preferred compositions are between 300 Jm-3 and about 9,000 J m-3, more preferably between 1,000 J m-3 and about8,000 J m-3, more preferably between 2,000 J m-3 and about 7,000 J m-3and most preferably between 2,500 J m-3 and about 6,000 J m-3, asdetermined by the AQUEOUS PHASE EXPRESSION TEST METHOD. These limitsallow for viable product compositions that—for example, provideevaporative and/or sensate-based cooling when the composition is appliedto the skin and cleaning when applied to a hard surface. These worklimits are in contrast to bar soaps and deodorant sticks that do notexpress aqueous phase when compressed. These work limits are also incontrast to gelatins that likewise do not express water when compressed.So, it is surprising that high-water compositions can be created withthese materials, that express aqueous phase with compression. Notwishing to be bound by theory, it is believed this a result of a networkof crystalline materials that break up during the application ofsufficient stress—releasing the aqueous phase with no uptake when thecompression is released.

Firmness

Firmness should be agreeable to consumer applications, in forming astructured rheological solid composition, with preferred embodimentsbetween about 0.5 N to about 25.0 N, more preferably between 1.0 N toabout 20.0 N, more preferably between 3.0 N to about 15.0 N and mostpreferably between 5.0 N and about 10.0 N. These firmness values allowfor viable product compositions that may retain their shape when restingon a surface, and as such are useful as a rheological solid stick toprovide a dry-to-the-touch but wet-to-the-push properties. The firmnessvalues are significantly softer than bar soaps and deodorants, whichexceed these values. So, it is surprising that high-water compositionscan be created that remain as rheological solid compositions withbetween about 0.25 wt % to about 10 wt % crystallizing agent, morepreferably between about 0.5 wt % to about 7 wt % crystallizing agentand most preferably between about 1 wt % to about 5 wt % crystallizingagent. Not wishing to be bound by theory, it is believed this a resultof crystallizing agent materials creating the interlocking mesh thatprovides sufficient firmness.

Thermal Stability

Thermal stability is used to ensure that the structured rheologicalsolid composition can be delivered as intended to the consumer throughthe supply chain, preferably with thermal stability greater than about40° C., more preferably greater than about 45° C. and most preferablygreater than about 50° C., as determined by the THERMAL STABILITY TESTMETHOD. Creating compositions with acceptable thermal stability isdifficult, as it may vary unpredictably with concentration of thecrystallizing agent and soluble active agent(s). Not wishing to be boundby theory, thermal stability results from the insolubility of thecrystallizing agent in the aqueous phase. Conversely, thermalinstability is thought to result from complete solubilization of thecrystallizing agent that comprised the mesh.

Chain Length Blends

Effective chain length blends allow the creation of effective meshmicrostructures in rheological solid compositions. In fact, adhoc (orinformed selection) of crystallizing agents often leads to liquid orvery soft compositions. The crystallizing agent may comprise a mixtureof sodium carboxylate molecules, where each molecule has a specificchain length. For example, sodium stearate has a chain length of 18,sodium oleate has a chain length of 18:1 (where the 1 reflects a doublebond in the chain), sodium palmitate has a chain length of 16, and soon. The chain length distribution—or the quantitative weight fraction ofeach chain length in the crystallizing agent, can be determined by theBLEND TEST METHOD, as described below. Commercial sources ofcrystallizing agent usually comprise complicated mixtures of molecules,often with chain lengths between 10 to 17.

Rheological solid compositions of the present invention have preferredchain length blends, as described by ‘Optimal Purity’ (Po) and ‘SinglePurity’ (Ps), determined by the BLEND TEST METHOD. Sodium carboxylatecrystallizing agents can have an ‘Optimal Chain Length’ of between 13 to22 carbons and can be used alone or combined to form mesh structuresthat satisfy all three performance criteria of a rheological solidcomposition. Not wishing to be bound by theory, it is believed thatthese chain length molecules (13 to 22) have a high solubilizationtemperature (e.g. Krafft Temperature) and can pack into crystalsefficiently. Sodium carboxylate crystallizing agents can have‘Unsuitable Chain Length’ crystallizing agents have chain length ofsodium carboxylate molecules of 10, 12, 18:1 and 18:2 (and shorter orother unsaturated chain lengths). When present in compositions alone orin some combinations with ‘optimal chain length’ molecules, they do notform rheological solid composition that meet the required performancecriteria. Accordingly, inventive compositions require the proper blendof crystallizing agent molecules, to ensure the proper properties of therheological solid composition. Po describes the total weight fraction ofoptimal chain length molecules of crystallizing agent to the totalweight of crystallizing agent molecules, that is preferably Po>0.4, morepreferably Po>0.6, more preferably Po>0.8 and most preferably Po>0.90.Ps describes the total weight fraction of the most common chain lengthmolecule in the crystallizing agent to the total weight of crystallizingagent, that is preferably Ps>0.5, more preferably Ps>0.6, morepreferably Ps>0.7, more preferably Ps>0.9.

Aqueous Phase

The rheological solid composition may include an aqueous carrier. Theaqueous carrier which is used may be distilled, deionized, or tap water.Water may be present in any amount for the rheological solid compositionto be an aqueous solution. Water may be present in an amount of about 80wt % to 99.5 wt %, alternatively about 90 wt % to about 99.5 wt %,alternatively about 92 wt % to about 99.5 wt %, alternatively about 95wt %, by weight of the rheological solid composition. Water containing asmall amount of low molecular weight monohydric alcohols, e.g., ethanol,methanol, and isopropanol, or polyols, such as ethylene glycol andpropylene glycol, can also be useful. However, the volatile lowmolecular weight monohydric alcohols such as ethanol and/or isopropanolshould be limited since these volatile organic compounds will contributeboth to flammability problems and environmental pollution problems. Ifsmall amounts of low molecular weight monohydric alcohols are present inthe rheological solid composition due to the addition of these alcoholsto such things as perfumes and as stabilizers for some preservatives,the level of monohydric alcohol may about 1 wt % to about 5 wt %,alternatively less than about 6 wt %, alternatively less than about 3 wt%, alternatively less than about 1 wt %, by weight of the rheologicalsolid composition.

However, other components can be optionally dissolved with the lowmolecular weight monohydric alcohols in the water to create an aqueousphase. Combined, these components are referred to as soluble activeagents. Such soluble active agents include, but are not limited to,catalysts, activators, peroxides, enzymes, antimicrobial agents,preservatives, sodium chloride, surfactants and polyols. Thecrystallizing agent and insoluble active agents may be dispersed in theaqueous phase.

Catalysts

In embodiments, soluble active agents can include one or more metalcatalysts. In embodiments, the metal catalyst can include one or more ofdichloro-1,4-diethyl-1,4,8,11-tetraaazabicyclo[6.6.2]hexadecanemanganese(II); anddichloro-1,4-dimethyl-1,4,8,11-tetraaazabicyclo[6.6.2]hexadecanemanganese(II). In embodiments, the non-metal catalyst can include one ormore of2-[3-[(2-hexyldodecyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolium,inner salt;3,4-dihydro-2-[3-[(2-pentylundecyl)oxy]-2-(sulfooxy)propyl]isoquinolinium,inner salt;2-[3-[(2-butyldecyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium,inner salt;3,4-dihydro-2-[3-(octadecyloxy)-2-(sulfooxy)propyl]isoquinolinium, innersalt; 2-[3-(hexadecyloxy)-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium,inner salt;3,4-dihydro-2-[2-(sulfooxy)-3-(tetradecyloxy)propyl]isoquinolinium,inner salt:2-[3-(dodecyloxy)-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium, innersalt;2-[3-[(3-hexyldecyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium,inner salt;3,4-dihydro-2-[3-[(2-pentylnonyl)oxy]-2-(sulfooxy)propyl]isoquinolinium,inner salt:3,4-dihydro-2-[3-[(2-propylheptyl)oxy]-2-(sulfooxy)propyl]isoquinolinium,inner salt;2-[3-[(2-butyloctyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium,inner salt;2-[3-(decyloxy)-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium, innersalt; 3,4-dihydro-2-[3-(octyloxy)-2-(sulfooxy)propyl]isoquinolinium,inner salt; and2-[3-[(2-ethylhexyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium,inner salt.

Activators

In embodiments, soluble active agent can include one or more activators.In embodiments, the activator can include one or more of tetraacetylethylene diamine (TAED); benzoylcaprolactam (BzCL);4-nitrobenzoylcaprolactam; 3-chlorobenzoylcaprolactam;benzoyloxybenzenesulphonate (BOBS): nonanoyloxybenzene¬sulphonate(NOBS); phenyl benzoate (PhBz); decanoyloxybenzenesulphonate (C₁₀-OBS);benzoylvalerolactam (BZVL); octanoyloxybenzenesulphonate (C₈-OBS);perhydrolyzable esters; 4-[N-(nonanoyl) amino hexanoyloxy]-benzenesulfonate sodium salt (NACA-OBS); dodecanoyloxybenzenesulphonate (LOBSor C₁₂-OBS); 10-undecenoyioxybenzenesulfonate (UDOBS or C₁₁-OBS withunsaturation in the 10 position); decanoyloxybenzoic acid (DOBA);(6-oclanamidocaproyl)oxybenzenesulfonate; (6-nonanamidocaproyl)oxybenzenesulfonate; and (6-decanamidocaproyl)oxybenzenesulfonate.

Peroxy-Carboxylic Acids

In embodiments, soluble active agent can include one or more preformedperoxy carboxylic acids. In embodiments, the peroxy carboxylic acids caninclude one or more of peroxymonosulfuric acids; perimidic acids;percabonic acids; percarboxilic acids and salts of said acids;pithalimidoperoxyhexanoic acid; amidoperoxyacids;1,12-diperoxydodecanedioic acid; and monoperoxyphthalic acid (magnesiumsalt hexahydrate), wherein said amidoperoxyacids may includeN,N′-terephthaloyl-di(6-amrinocaproic acid), a monononylamide of eitherperoxysuccinic acid (NAPSA) or of peroxyadipic acid (NAPAA), orN-nonanoylaminoperoxycaproic acid (NAPCA).

In embodiments, water-based and/or water soluble benefit agent caninclude one or more diacyl peroxide. In embodiments, the diacyl peroxidecan include one or more of dinonanoyl peroxide, didecanoyl peroxide,diundecanoyl peroxide, dilauroyl peroxide, and dibenzoyl peroxide,di-(3,5,5-trimethyl hexanoyl) peroxide, wherein said diacyl peroxide canbe clatharated.

Peroxides

In embodiments, soluble active agent can include one or more hydrogenperoxide. In embodiments, hydrogen peroxide source can include one ormore of a perborate, a percarbonate a peroxyhy drate, a peroxide, apersulfate and mixtures thereof, in one aspect said hydrogen peroxidesource may comprise sodium perborate, in one aspect said sodiumperborate may comprise a mono- or tetra-hydrate, sodium pyrophosphateperoxyhydrate, urea peroxyhydrate, trisodium phosphate peroxyhydrate,and sodium peroxide.

Enzymes

In embodiments, soluble active agent can include one or more enzymes. Inembodiment, the enzyme can include one or more of peroxidases,proteases, lipases, phospholipases, cellulases, cellobiohydrolases,cellobiose dehydrogenases, esterases, cutinases, pectinases, mannanases,pectate lyases, keratinases, reductases, oxidases, phenoloxidases,lipoxygenases, ligninases, pullulanases, tannases, pentosanases,glucanases, arabinosidases, hyaluronidase, chondroitinase, laccases,amylases, and dnases.

Sensate

In embodiments, soluble active agent can include one or more componentsthat provide a sensory benefit, often called a sensate. Sensates canhave sensory attributes such as a warming, tingling or coolingsensation. Suitable sensates include, for example, menthol, menthyllactate, leaf alcohol, camphor, clove bud oil, eucalyptus oil, anethole,methyl salicylate, eucalyptol, cassia, 1-8 menthyl acetate, eugenol,oxanone, alpha-irisone, propenyl guaethol, thymol, linalool,benzaldehyde, cinnamaldehyde glycerol acetal known as CGA, Winsense WS-5supplied by Renessenz-Symrise, Vanillyl butyl ether known as VBE, andmixtures thereof.

In certain embodiments, the sensate comprises a coolant. The coolant canbe any of a wide variety of materials. Included among such materials arecarboxamides, menthol, ketals, diols, and mixtures thereof. Someexamples of carboxamide coolants include, for example, paramenthancarboxyamide agents such as N-ethyl-p-menthan-3-carboxamide, knowncommercially as “WS-3”, N,2,3-trimethyl-2-isopropylbutanamide, known as“WS-23,” and N-(4-cyanomethylphenyl)-ρ-menthanecarboxamide, known asG-180 and supplied by Givaudan. G-180 generally comes as a 7.5% solutionin a flavor oil, such as spearmint oil or peppermint oil. Examples ofmenthol coolants include, for example, menthol;3-1-menthoxypropane-1,2-diol known as TK-10, manufactured by Takasago;menthone glycerol acetal known as MGA manufactured by Haarmann andReimer; and menthyl lactate known as Frescolatt manufactured by Haarmannand Reimer. The terms menthol and menthyl as used herein include dextro-and levorotatory isomers of these compounds and racemic mixturesthereof.

In certain embodiments, the sensate comprises a coolant selected fromthe group consisting of menthol; 3-1-menthoxypropane-1,2-diol, menthyllactate; N,2,3-trimethyl-2-isopropylbutanamide;N-ethyl-p-menthan-3-carboxamide;N-(4-cyanomethylphenyl)-ρ-menthanecarboxamide, and combinations thereof.In further embodiments, the sensate comprises menthol;N,2,3-trimethyl-2-isopropylbutanamide.

Surfactant

Detersive Surfactant: Suitable detersive surfactants include anionicdetersive surfactants, non-ionic detersive surfactant, cationicdetersive surfactants, zwitterionic detersive surfactants and amphotericdetersive surfactants and mixtures thereof. Suitable detersivesurfactants may be linear or branched, substituted or un-substituted,and may be derived from petrochemical material or biomaterial. Preferredsurfactant systems comprise both anionic and nonionic surfactant,preferably in weight ratios from 90:1 to 1:90. In some instances aweight ratio of anionic to nonionic surfactant of at least 1:1 ispreferred. However, a ratio below 10:1 may be preferred.

When present, the total surfactant level is preferably from 0.1% to 60%,from 1% to 50% or even from 5% to 40% by weight of the subjectcomposition.

Anionic detersive surfactant: Anionic surfactants include, but are notlimited to, those surface-active compounds that contain an organichydrophobic group containing generally 8 to 22 carbon atoms or generally8 to 18 carbon atoms in their molecular structure and at least onewater-solubilizing group preferably selected from sulfonate, sulfate,and carboxylate so as to form a water-soluble compound. Usually, thehydrophobic group will comprise a C8-C22 alkyl, or acyl group. Suchsurfactants are employed in the form of water-soluble salts and thesalt-forming cation usually is selected from sodium, potassium,ammonium, magnesium and mono-, with the sodium cation being the usualone chosen.

Anionic surfactants of the present invention and adjunct anioniccosurfactants, may exist in an acid form, and said acid form may beneutralized to form a surfactant salt which is desirable for use in thepresent compositions. Typical agents for neutralization include themetal counterion base such as hydroxides, e.g., NaOH or KOH. Furtherpreferred agents for neutralizing anionic surfactants of the presentinvention and adjunct anionic surfactants or cosurfactants in their acidforms include ammonia, amines, oligamines, or alkanolamines.Alkanolamines are preferred. Suitable non-limiting examples includingmonoethanolamine, diethanolamine, triethanolamine, and other linear orbranched alkanolamines known in the art; for example, highly preferredalkanolamines include 2-amino-1-propanol, 1-aminopropanol,monoisopropanolamine, or 1-amino-3-propanol. Amine neutralization may bedone to a full or partial extent, e.g. part of the anionic surfactantmix may be neutralized with sodium or potassium and part of the anionicsurfactant mix may be neutralized with amines or alkanolamines.

Suitable sulphonate detersive surfactants include methyl estersulphonates, alpha olefin sulphonates, alkyl benzene sulphonates,especially alkyl benzene sulphonates, preferably C10-13 alkyl benzenesulphonate. Suitable alkyl benzene sulphonate (LAS) is obtainable,preferably obtained, by sulphonating commercially available linear alkylbenzene (LAB). Suitable LAB includes low 2-phenyl LAB, such as thosesupplied by Sasol under the tradename Isochem® or those supplied byPetresa under the tradename Petrelab®, other suitable LAB include high2-phenyl LAB, such as those supplied by Sasol under the tradenameHyblene®. A suitable anionic detersive surfactant is alkyl benzenesulphonate that is obtained by DETAL catalyzed process, although othersynthesis routes, such as HF, may also be suitable. In one aspect amagnesium salt of LAS is used

Suitable sulphate detersive surfactants include alkyl sulphate,preferably C₈₋₁₈ alkyl sulphate, or predominantly C₁₂ alkyl sulphate.

A preferred sulphate detersive surfactant is alkyl alkoxylated sulphate,preferably alkyl ethoxylated sulphate, preferably a C₈₋₁₈ alkylalkoxylated sulphate, preferably a C₈₋₁₈ alkyl ethoxylated sulphate,preferably the alkyl alkoxylated sulphate has an average degree ofalkoxylation of from 0.5 to 20, preferably from 0.5 to 10, preferablythe alkyl alkoxylated sulphate is a C₈₋₁₈ alkyl ethoxylated sulphatehaving an average degree of ethoxylation of from 0.5 to 10, preferablyfrom 0.5 to 5, more preferably from 0.5 to 3. The alkyl alkoxylatedsulfate may have a broad alkoxy distribution or a peaked alkoxydistribution.

The alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzenesulphonates may be linear or branched, including 2 alkyl substituted ormid chain branched type, substituted or un-substituted, and may bederived from petrochemical material or biomaterial. Preferably, thebranching group is an alkyl. Typically, the alkyl is selected frommethyl, ethyl, propyl, butyl, pentyl, cyclic alkyl groups and mixturesthereof. Single or multiple alkyl branches could be present on the mainhydrocarbyl chain of the starting alcohol(s) used to produce thesulfated anionic surfactant used in the compositions of the invention.Most preferably the branched sulfated anionic surfactant is selectedfrom alkyl sulfates, alkyl ethoxy sulfates, and mixtures thereof.

Alkyl sulfates and alkyl alkoxy sulfates are commercially available witha variety of chain lengths, ethoxylation and branching degrees.Commercially available sulfates include those based on Neodol alcoholsex the Shell company, Lial—Isalchem and Safol ex the Sasol company,natural alcohols ex The Procter & Gamble Chemicals company.

Other suitable anionic detersive surfactants include alkyl ethercarboxylates.

Non-ionic detersive surfactant: Suitable non-ionic detersive surfactantsare selected from the group consisting of: C₈-C₁₈ alkyl ethoxylates,such as, NEODOL® non-ionic surfactants from Shell; C₆-C₁₂ alkyl phenolalkoxylates wherein preferably the alkoxylate units are ethyleneoxyunits, propyleneoxy units or a mixture thereof: C₁₂-C₁₈ alcohol andC₆-C₁₂ alkyl phenol condensates with ethylene oxide/propylene oxideblock polymers such as Pluronic® from BASF; alkylpolysaccharides,preferably alkylpolyglycosides; methyl ester ethoxylates; polyhydroxyfatty acid amides; ether capped poly(oxyalkylated) alcohol surfactants;and mixtures thereof.

Suitable non-ionic detersive surfactants are alkylpolyglucoside and/oran alkyl alkoxylated alcohol.

Suitable non-ionic detersive surfactants include alkyl alkoxylatedalcohols, preferably C₈₋₁₈ alkyl alkoxylated alcohol, preferably a C₈₋₁₈alkyl ethoxylated alcohol, preferably the alkyl alkoxylated alcohol hasan average degree of alkoxylation of from 1 to 50, preferably from 1 to30, or from 1 to 20, or from 1 to 10, preferably the alkyl alkoxylatedalcohol is a C₈₋₁₈ alkyl ethoxylated alcohol having an average degree ofethoxylation of from 1 to 10, preferably from 1 to 7, more preferablyfrom 1 to 5 and most preferably from 3 to 7. The alkyl alkoxylatedalcohol can be linear or branched, and substituted or un-substituted.Suitable nonionic surfactants include those with the trade nameLutensol® from BASF.

Cationic detersive surfactant: Suitable cationic detersive surfactantsinclude alkyl pyridinium compounds, alkyl quaternary ammonium compounds,alkyl quaternary phosphonium compounds, alkyl ternary sulphoniumcompounds, and mixtures thereof.

Preferred cationic detersive surfactants are quaternary ammoniumcompounds having the general formula:

(R)(R₁)(R₂)(R₃)N⁺X⁻

wherein, R is a linear or branched, substituted or unsubstituted C₆₋₁₈alkyl or alkenyl moiety, R₁ and R₂ are independently selected frommethyl or ethyl moieties, R₃ is a hydroxyl, hydroxymethyl or ahydroxyethyl moiety, X is an anion which provides charge neutrality,preferred anions include: halides, preferably chloride; sulphate; andsulphonate.

Amphoteric and Zwitterionic detersive surfactant: Suitable amphoteric orzwitterionic detersive surfactants include amine oxides, and/orbetaines. Preferred amine oxides are alkyl dimethyl amine oxide or alkylamido propyl dimethyl amine oxide, more preferably alkyl dimethyl amineoxide and especially coco dimethyl amino oxide. Amine oxide may have alinear or mid-branched alkyl moiety. Typical linear amine oxides includewater-soluble amine oxides containing one R1 C8-18 alkyl moiety and 2 R2and R3 moieties selected from the group consisting of C1-3 alkyl groupsand C1-3 hydroxyalkyl groups. Preferably amine oxide is characterized bythe formula R1-N(R2)(R3)O wherein R1 is a C8-18 alkyl and R2 and R3 areselected from the group consisting of methyl, ethyl, propyl, isopropyl,2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl. The linear amineoxide surfactants in particular may include linear C10-C18 alkyldimethyl amine oxides and linear C8-C12 alkoxy ethyl dihydroxy ethylamine oxides.

Other suitable surfactants include betaines, such as alkyl betaines,alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (INCI Sultaines)as well as Phosphobetaines

Antimicrobial Compounds

In embodiments, soluble active agent can include an effective amount ofa compound for reducing the number of viable microbes in the air or oninanimate surfaces. Antimicrobial compounds are effective on gramnegative or gram positive bacteria or fungi typically found on indoorsurfaces that have contacted human skin or pets such as couches,pillows, pet bedding, and carpets. Such microbial species includeKlebsiella pneumoniae, Staphylococcus aureus, Aspergillus niger,Klebsiella pneumoniae, Steptococcus pyogenes, Salmonella choleraesuis,Escherichia coli, Trichophyton mentagrophytes, and Pseudomonoasaeruginosa. The antimicrobial compounds may also be effective atreducing the number of viable viruses such H1-N1, Rhinovirus,Respiratory Syncytial, Poliovirus Type 1, Rotavirus, Influenza A, Herpessimplex types 1 & 2, Hepatitis A, and Human Coronavirus.

Antimicrobial compounds suitable in the rheological solid compositioncan be any organic material which will not cause damage to fabricappearance (e.g., discoloration, coloration such as yellowing,bleaching). Water-soluble antimicrobial compounds include organic sulfurcompounds, halogenated compounds, cyclic organic nitrogen compounds, lowmolecular weight aldehydes, quaternary compounds, dehydroacetic acid,phenyl and phenoxy compounds, or mixtures thereof.

A quaternary compound may be used. Examples of commercially availablequaternary compounds suitable for use in the rheological solidcomposition are Barquat available from Lonza Corporation; and didecyldimethyl ammonium chloride quat under the trade name Bardac® 2250 fromLonza Corporation.

The antimicrobial compound may be present in an amount from about 500ppm to about 7000 ppm, alternatively about 1000 ppm to about 5000 ppm,alternatively about 1000 ppm to about 3000 ppm, alternatively about 1400ppm to about 2500 ppm, by weight of the rheological solid composition.

Preservatives

In embodiments, soluble active agent can include a preservative. Thepreservative may be present in an amount sufficient to prevent spoilageor prevent growth of inadvertently added microorganisms for a specificperiod of time, but not sufficient enough to contribute to the odorneutralizing performance of the rheological solid composition. In otherwords, the preservative is not being used as the antimicrobial compoundto kill microorganisms on the surface onto which the rheological solidcomposition is deposited in order to eliminate odors produced bymicroorganisms. Instead, it is being used to prevent spoilage of therheological solid composition in order to increase the shelf-life of therheological solid composition.

The preservative can be any organic preservative material which will notcause damage to fabric appearance, e.g., discoloration, coloration,bleaching. Suitable water-soluble preservatives include organic sulfurcompounds, halogenated compounds, cyclic organic nitrogen compounds, lowmolecular weight aldehydes, parabens, propane diol materials,isothiazolinones, quaternary compounds, benzoates, low molecular weightalcohols, dehydroacetic acid, phenyl and phenoxy compounds, or mixturesthereof.

Non-limiting examples of commercially available water-solublepreservatives include a mixture of about 77%5-chloro-2-methyl-4-isothiazolin-3-one and about 23%2-methyl-4-isothiazolin-3-one, a broad spectrum preservative availableas a 1.5% aqueous solution under the trade name Kathon® CG by Rohm andHaas Co.; 5-bromo-5-nitro-1,3-dioxane, available under the tradenameBronidox L® from Henkel; 2-bromo-2-nitropropane-1,3-diol, availableunder the trade name Bronopol® from Inolex; 1,1′-hexamethylenebis(5-(p-chlorophenyl)biguanide), commonly known as chlorhexidine, andits salts, e.g., with acetic and digluconic acids; a 95:5 mixture of1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione and3-butyl-2-iodopropynyl carbamate, available under the trade name GlydantPlus® from Lonza;N-[1,3-bis(hydroxymethyl)2,5-dioxo-4-imidazolidinyl]-N,N′-bis(hydroxy-methyl)urea, commonly known as diazolidinyl urea, available under the tradename Germall® II from Sutton Laboratories, Inc.;N,N″-methylenebis{N′-[1-(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]urea},commonly known as imidazolidinyl urea, available, e.g., under the tradename Abiol® from 3V-Sigma, Unicide U-13® from Induchem, Germall 115®from Sutton Laboratories, Inc.; polymethoxy bicyclic oxazolidine,available under the trade name Nuosept® C from Hils America;formaldehyde; glutaraldehyde; polyaminopropyl biguanide, available underthe trade name Cosmocil CQ® from ICI Americas, Inc., or under the tradename Mikrokill® from Brooks, Inc; dehydroacetic acid; andbenzsiothiazolinone available under the trade name Koralone™ B-119 fromRohm and Hass Corporation; 1,2-Benzisothiazolin-3-one; Acticide MBS.

Suitable levels of preservative are from about 0.0001 wt. % to about 0.5wt. %, alternatively from about 0.0002 wt. % to about 0.2 wt. %,alternatively from about 0.0003 wt. % to about 0.1 wt. %, by weight ofthe rheological solid composition.

Adjuvants

Adjuvants can be added to the rheological solid composition herein fortheir known purposes. Such adjuvants include, but are not limited to,water soluble metallic salts, including zinc salts, copper salts, andmixtures thereof; antistatic agents; insect and moth repelling agents;colorants; antioxidants; aromatherapy agents and mixtures thereof.

The compositions of the present invention can also comprise any additiveusually used in the field under consideration. For example,non-encapsulated pigments, film forming agents, dispersants,antioxidants, essential oils, preserving agents, fragrances, liposolublepolymers that are dispersible in the medium, fillers, neutralizingagents, silicone elastomers, cosmetic and dermatological oil-solubleactive agents such as, for example, emollients, moisturizers, vitamins,anti-wrinkle agents, essential fatty acids, sunscreens, and mixturesthereof can be added.

Solvents

The composition can contain a solvent. Non-limiting examples of solventscan include ethanol, glycerol, propylene glycol, polyethylene glycol400, polyethylene glycol 200, and mixtures thereof. In one example thecomposition comprises from about 0.5% to about 15% solvent, in anotherexample from about 1.0% to about 10% solvent, and in another examplefrom about 1.0% to about 8.0% solvent, and in another example from about1% solvent to about 5% solvent.

Vitamins

As used herein, “xanthine compound” means one or more xanthines,derivatives thereof, and mixtures thereof. Xanthine Compounds that canbe useful herein include, but are not limited to, caffeine, xanthine,1-methyl xanthine, theophylline, theobromine, derivatives thereof, andmixtures thereof. Among these compounds, caffeine is preferred in viewof its solubility in the composition. The composition can contain fromabout 0.05%, preferably from about 2.0%, more preferably from about0.1%, still more preferably from about 1.0%, and to about 0.2%,preferably to about 1.0%, more preferably to about 0.3% by weight of axanthine compound

As used herein, “vitamin B3 compound” means a one or more compoundshaving the formula:

wherein R is —CONH₂ (i.e., niacinamide), —COOH (i.e., nicotinic acid) or—CH₂OH (i.e., nicotinyl alcohol); derivatives thereof; mixtures thereof;and salts of any of the foregoing.

Exemplary derivatives of the foregoing vitamin B3 compounds includenicotinic acid esters, including non-vasodilating esters of nicotinicacid (e.g, tocopherol nicotinate, and myristyl nicotinate), nicotinylamino acids, nicotinyl alcohol esters of carboxylic acids, nicotinicacid N-oxide and niacinamide N-oxide. The composition can contain fromabout 0.05%, preferably from about 2.0%, more preferably from about0.1%, still more preferably from about 1.0%, and to about 0.1%,preferably to about 0.5%, more preferably to about 0.3% by weight of avitamin B3 compound

As used herein, the term “panthenol compound” is broad enough to includepanthenol, one or more pantothenic acid derivatives, and mixturesthereof panthenol and its derivatives can include D-panthenol([R]-2,4-dihydroxy-N-[3-hydroxypropyl)]-3,3-dimethylbutamide),DL-panthenol, pantothenic acids and their salts, preferably the calciumsalt, panthenyl triacetate, royal jelly, panthetine, pantotheine,panthenyl ethyl ether, pangamic acid, pantoyl lactose, vitamin Bcomplex, or mixtures thereof. The composition can contain from about0.01%, preferably from about 0.02%, more preferably from about 0.05%,and to about 3%, preferably to about 1%, more preferably to about 0.5%by weight of a panthenol compound

Sodium chloride (and other sodium salts) is a particular useful additiveto the aqueous phase to adjust the thermal stability of compositions,but must be added into the composition with particular care (Example 3).Not wishing to be bound by theory, sodium chloride is thought to ‘saltout’ inventive crystallizing agents decreasing their solubility. Thishas the effect of increasing the thermal stability temperature of therheological solid composition as measured by the THERMAL STABILITY TESTMETHOD. For example, Optimal Chain Length crystallizing agents can havethe thermal stability temperatures increased as much as 15° C. withsodium chloride addition. This is particularly valuable as the additionof other ingredients into the aqueous phase often lower the thermalstability temperature in the absence of sodium chloride. Surprisingly,adding sodium chloride can lead to adverse effects in the preparation ofthe rheological solid compositions. It is preferable in most makingprocesses, to add sodium chloride into the hot crystallizing agentaqueous phase before cooling to form the mesh. However, adding too muchmay cause ‘curding’ of the crystallizing agents and absolutely horridcompositions. The sodium chloride may also be added after the formationof the mesh, to provide the benefit of raising the thermal stabilitytemperature at higher levels without curding. Finally, while the thermalstability temperature is increased with addition of sodium chloride, theaddition of other non-sodium salts changes the fibrous nature of thecrystals formed from the crystallizing agents, to form plates orplatelet crystals, which are not rheological solids.

Rheological Solid Composition Properties

Stability Temperature

Stability temperature, as used herein, is the temperature at which mostor all of the crystallizing agent completely dissolves into an aqueousphase, such that a composition no longer exhibits a stable solidstructure and may be considered a liquid. In embodiments of the presentinvention the stability temperature range may be from about 40° C. toabout 95° C., about 40° C. to about 90° C., about 50° C. to about 80°C., or from about 60° C. to about 70° C., as these temperatures aretypical in a supply chain. Stability temperature can be determined usingthe THERMAL STABILITY TEST METHOD, as described below.

Firmness

Depending on the intended application, such as a stick, firmness of thecomposition may also be considered. The firmness of a composition may,for example, be expressed in Newtons of force. For example, compositionsof the present invention comprising 1-3 wt % crystallizing agent maygive values of about 4-about 12 N, in the form of a solid stick orcoating on a sheet. As is evident, the firmness of the compositionaccording to embodiments of the present invention may, for example, besuch that the composition is advantageously self-supporting and canrelease liquids and/or actives upon application of low to moderateforce, for example upon contact with a surface, to form a satisfactorydeposit on a surface, such as the skin and/or superficial body growths,such as keratinous fibers. In addition, this hardness may impart goodimpact strength to the inventive compositions, which may be molded orcast, for example, into stick or sheet form, such as a wipe or dryersheet product. The composition of the invention may also be transparentor clear, including for example, a composition without pigments.Preferred firmness is between about 0.1 N to about 50.0 N, morepreferably between about 0.5 N to about 40.0 N, more preferably betweenabout 1.0 N to about 30.0 N and most preferably between about 2.5 N toabout 15.0 N. The firmness may be measured using the FIRMNESS TESTMETHOD, as described below.

Aqueous Phase Expression

Depending on the intended application, such as a stick, aqueous phaseexpression of the composition may also be considered. This is a measureof the amount of work need per unit volume to express the aqueous phasefrom the compositions, with larger values meaning it becomes moredifficult to express liquid. A low value might be preferred, forexample, when applying the composition to the skin. A high value mightbe preferred, for example, when the composition is applied to asubstrate that requires ‘dry-to-the-touch-but-wet-to-the-wipe’properties. Preferred values are between about 100 J m-3 to about 8,000J m-3, more preferably between about 1,000 J m-3 to about 7,000 J m-3,and most preferably between about 2,000 J m-3 to about 5,000 J m-3. Theliquid expression may be measured using the AQUEOUS PHASE EXPRESSIONTEST METHOD, as described herein.

Firmness Test Method

All samples and procedures are maintained at room temperature (25±3° C.)prior to and during testing, with care to ensure little or no waterloss.

All measurements were made with a TA-XT2 Texture Analyzer (TextureTechnology Corporation, Scarsdale, N.Y., U.S.A.) outfitted with astandard 450 angle penetration cone tool (Texture Technology Corp., aspart number TA-15).

To operate the TA-XT2 Texture Analyzer, the tool is attached to theprobe carrier arm and cleaned with a low-lint wipe. The sample ispositioned and held firmly such that the tool will contact arepresentative region of the sample. The tool is reset to be about 1 cmabove the product sample.

The sample is re-position so that the tool will contact a secondrepresentative region of the sample. A run is done by moving the tool ata rate of 2 mm/second exactly 10 mm into the sample. The “RUN” button onthe Texture Analyzer can be pressed to perform the measurement. A secondrun is done with the same procedure at another representative region ofthe sample at sufficient distance from previous measurements that theydo not affect the second run. A third run is done with the sameprocedure at another representative region of the sample at sufficientdistance from previous measurements that they do not affect the thirdrun.

The results of the FIRMNESS TEST METHOD, are all entered in the examplesin the row entitles ‘Firmness’. In general, the numeric value isreturned as the average of the maximum value of three measurements asdescribed above, except in one of the two cases:

1) the composition does not form a homogenous rheological solid (e.g.completely or partially liquid), the value of ‘NMT’ is returned;

2) and, the composition curds during making, the value of ‘NM2’ isreturned.

Thermal Stability Test Method

All samples and procedures are maintained at room temperature (25±3° C.)prior to testing.

Sampling is done at a representative region on the sample, in two steps.First, a spatula is cleaned with a laboratory wipe and a small amount ofthe sample is removed and discarded from the top of the sample at theregion, to create a small square hole about 5 mm deep. Second, thespatula is cleaned again with a clean laboratory wipe, and a smallamount of sample is collected from the square hole and loaded into DSCpan.

The sample is loaded into a DSC pan. All measurements are done in ahigh-volume-stainless-steel pan set (TA part #900825.902). The pan, lidand gasket are weighed and tared on a Mettler Toledo MT5 analyticalmicrobalance (or equivalent; Mettler Toledo, LLC., Columbus, Ohio). Thesample is loaded into the pan with a target weight of 20 mg (+/−10 mg)in accordance with manufacturer's specifications, taking care to ensurethat the sample is in contact with the bottom of the pan. The pan isthen sealed with a TA High Volume Die Set (TA part #901608.905). Thefinal assembly is measured to obtain the sample weight.

The sample is loaded into TA Q Series DSC (TA Instruments, New Castle,Del.) in accordance with the manufacture instructions. The DSC procedureuses the following settings: 1) equilibrate at 25° C.; 2) mark end ofcycle 1; 3) ramp 1.00° C./min to 90.00° C.; 4) mark end of cycle 3; then5) end of method; Hit run.

The results of the TEMPERATURE STABILITY TEST METHOD, are all entered inthe examples in the row entitles ‘Temperature’. In general, the numericvalue is returned as described above, except in one of the two cases:

1) the composition does not form a homogenous rheological solid (e.g.completely or partially liquid) and is not suitable for the measurement,the value of ‘NM3’ is returned;

2) and, the composition curds during making and is not suitable for themeasurement, the value of ‘NM4’ is returned.

Aqueous Phase Expression Test Method

All samples and procedures are maintained at room temperature 25 (±3°C.) prior to testing.

Measurements for the determination of aqueous phase expression were madewith a TA Discovery HR-2 Hybrid Rheometer (TA Instruments, New Castle,Del.) and accompanying TRIOS software version 3.2.0.3877, or equivalent.The instrument is outfitted with a DHR Immobilization Cell (TAInstrument) and 55 mm flat steel plate (TA Instruments). The calibrationis done in accordance with manufacturer's recommendations, with specialattention to measuring the bottom of the DHR Immobilization Cell, toensure this is established as gap=0.

Samples are prepared in accordance with EXAMPLE procedures. It iscritical that the sample be prepared in Speed Mixer containers(Flak-Tech, Max 60 Cup Translucent, Cat #501 222t), so that the diameterof the sample matches the diameter of the HR-2 Immobilization Cell. Thesample is released from the containers by running a thin spatula betweenthe edge of the container and the sample. The container is gently turnedover and placed on a flat surface. A gentle force is applied to thecenter of the bottom of the overturned container, until the samplereleases and gently glides out of the container. The sample is carefullyplaced in the center ring of the DHR Immobilization Cell. Care is usedto ensure that the sample is not deformed and re-shaped through thisentire process. The diameter of the sample should be slightly smallerthan the inner diameter of the ring. This ensures that force applied tothe sample in latter steps does not significantly deform the cylindricalshape of the sample, instead allowing the aqueous phase to escapethrough the bottom of the sample. This also ensures that any change inthe height of the sample for the experiment is equivalent to the amountof aqueous phase expressed during the test. At the end of themeasurement, one should confirm that the aqueous phase is indeedexpressed from the sample through the measurement, by looking foraqueous phase in the effluent tube connected to the Immobilization Cell.If no aqueous phase is observed, the sample is deemed not to expressaqueous phase and is not inventive.

Set the instrument settings as follows. Select Axial Test Geometry.Then, set “Geometry” options: Diameter=50 mm; Gap=45000 um; LoadingGap=45000 um; Trim Gap Offset=50 um; Material=‘Steel’; EnvironmentalSystem=“Peltier Plate”. Set “Procedure” options: Temperature=25° C.;Soak Time=0 sec; Duration=2000 sec; Motor Direction=“Compression”;Constant Linear Rate=2 um sec-1; Maximum Gap Change=0 um; Torque=0 uN m;Data Acquisition=‘save image’ every 5 sec.

Manually move the steel tool within about 1000 um of the surface of thesample, taking care that the tool does not touch the surface. In the“Geometry” options, reset Gap to this distance.

Start the run.

The data is expressed in two plots:

1) Plot 1: Axial Force (N) on the left-y-axis and Step Time (s) on thex-axis;

2) Plot 2: Gap (um) on the right-y-axis and Step Time (s) on the x-axis.

The Contact Time—T(contact), is obtained from Plot 1. The T(contact) isdefined as the time when the tool touches the top of the sample. TheT(contact) is the Step Time when the first Axial Force data pointexceeds 0.05 N.

The Sample Thickness—L, is the gap distance at the Contact Time, andexpressed in units of meters.

The Time of Compression—T(compression), is the Step Time at which thegap is 0.85*L, or 15% of the sample.

The Work required to squeeze the aqueous phase from the structure is thearea under the Axial Force curve in Plot 1 between T(contact) andT(compression) multiplied by Constant Linear Rate, or 2e-6 m s-1normalized by dividing the total volume of expressed fluids, and isexpressed in units of Joules per cubic meter (J m-3).

The results of the AQUEOUS PHASE EXPRESSION TEST METHOD, are all enteredin the examples in the row entitled ‘AP Expression’. In general, thenumeric value, as the average of at least two values is returned asdescribed, except in one of the three cases:

1) the composition does not form a homogenous rheological solid (e.g.completely or partially liquid) and is not suitable for the measurement,the value of ‘NM5’ is returned;

2) the composition curds during making and is not suitable for themeasurement, the value of ‘NM6’ is returned;

3) the composition is a rheological solid but too soft to effectivelyload in the device, the value of ‘NM7’ is returned;

4) and the composition is too hard so that the force exceeds 50 N beforethe 15% compression, the value of ‘NM8’ is returned;

Blend Test Method

All samples and procedures are maintained at room temperature 25 (±3°C.) prior to testing.

Samples are prepared by weighing 4 mg (+/−1 mg) of a 3% fatty acid inwater solution into a scintillation vial with a PTFE septum and thenadding 2 mL of ethanol ACS grade or equivalent. A cap is then placed onthe vial and the sample is mixed until the sample is homogenous. Thevial is then placed in a 70° C. oven with the cap removed to evaporatethe ethanol (and water), after which it is allowed to cool to roomtemperature.

A pipettor is used to dispense 2 mL of BF3-methanol (10% BoronTrifluoride in methanol, Sigma Aldrich #15716) into the vial, and thecapped tightly. The sample is placed on a VWR hot plate set at 70° C.until the sample is homogenous, and then for an additional 5 min beforecooling to room temperature.

A saturated sodium chloride solution is prepared by adding sodiumchloride salt ACS grade or equivalent to 10 mL of distilled water atambient temperature. Once the vial is at room temperature, 4 mL of thesaturated sodium chloride solution are added to the vial and swirled tomix. Then, 4 mL of hexane, ACS grade or equivalent, are added to thevial which is then capped and shaken vigorously. The sample is thenplaced on a stationary lab bench and until the hexane and water separateinto two phases.

A transfer pipet is used to transfer the hexane layer into a new 8 mLvial, and then 0.5 g of sodium sulfate, ACS grade or equivalent, isadded to dry the hexane layer. The dried hexane layer is thentransferred to a 1.8 mL GC vial for analysis.

Samples are analyzed using an Agilent 7890B (Agilent Technologies Inc.,Santa Carla, Calif.), or equivalent gas chromatograph, equipped withcapillary inlet system and flame ionization detector with peakintegration capabilities, and an Agilent DB-FastFAME (#G3903-63011), orequivalent column.

The gas chromatograph conditions and settings are defined as follows:uses Helium UHP grade, or regular grade helium purified through gaspurification system, as a carrier gas, and is set at a constant flowmode of 1.2 mL/minute (velocity of 31.8 cm/sec); has an oven temperatureprogram that is set for 100° C. for 2 minutes, and increased at a rateof 10° C. per minute until it reaches 250 C for 3 minutes; the injectortemperature is set to 250° C. and the detector temperature is set to280° C.; the gas flows are set to 40 mL/minute for hydrogen, 400mL/minute for air, and 25 mL/minute for the Make-up (helium); and theinjection volume and split ratio is defined a 1 uL, split 1:100injection.

The instrument is calibrated using a 37-Component FAME standard mixture(Supelco #CRM47885), or equivalent calibration standard. The ResponseFactor and Normalized Response Factor based on n-C16 FAME standard.

Response Factor is calculated for each component by dividing the FAMEFID Area account of an analyte in the calibration solution by theconcentration of the identical FAME analyte in the calibration solution.

The Normalized Response Factor is calculated by dividing the ResponseFactor of each component by the Response Factor of n-C16 methyl esterthat has been defined as 1.00.

The Normalized FAME FID Area is calculated with the Normalized ResponseFactor by dividing the FAME FID area (component) by the NormalizedResponse Factor (component).

The FAME weight percent of each component is calculated by dividing theNormalized FAME FID area (component) by the Normalized FAME FID area(total of each component) and then multiplying by one hundred.

The Conversion Factor from FAME to free Fatty Acid is calculated bydividing the Molecular Weight of the Target Fatty Acid by the MolecularWeight of the Target FAME.

The Normalized Fatty Acid FID Area is calculated by multiplying theNormalized FAME FID Area by the Conversion Factor from FAME to freeFatty Acid.

The Fatty Acid Weight Percent of each component is calculated bydividing the Normalized Fatty Acid FID Area (component) by theNormalized FA FID Area (total of each component) and the multiplying theresult by one hundred.

The Conversion Factor from FAME to free Fatty Acid Sodium Salt iscalculated by dividing the Molecular Weight of the Target Fatty AcidSodium Salt by the molecular weight of the Target FAME.

The Normalized Fatty Acid Sodium Salt FID Area is calculated bymultiplying the Normalized FAME FID Area by the Conversion Factor fromFAME to free Fatty Acid Sodium Salt.

The Weight percent of each Fatty Acid Sodium Salt component wascalculated by dividing the normalized Fatty Acid Sodium Salt FID area(component) by the Normalized Fatty Acid Sodium Salt FID area (total ofeach component) and then multiplying by one hundred.

Purity of the crystallizing agent is described in the following ways:

Optimal Purity—Po, which is the mass fraction of the optimal chainlength molecules in the crystallizing agent blend calculated as:

${Po} = \frac{\Sigma Mo}{Mt}$

where Mo is the mass of each optimal chain length in the crystallizingagent and Mt is the total mass of the crystallizing agent.

Single Purity—Ps, which is the mass fraction of the most common chainlength in the crystallizing agent blend calculated as:

${Ps} = \frac{Ms}{Mt}$

where Ms is the mass of the most common chain length in thecrystallizing agent and Mt is the total mass of the crystallizing agent.The value is expressed in brackets—[Ms], if the most common chain lengthis selected from the group of unsuitable chain length molecules.

EXAMPLES

Materials List

(1) Water: Millipore, Burlington, Mass. (18 m-ohm resistance)

(2) Sodium caprate (sodium decanoate, NaCl0): TCI Chemicals, Cat #D0024

(3) Sodium laurate (sodium dodecanoate, NaCl2): TCI Chemicals, Cat#D0024

(4) Sodium myristate (sodium tetradecanoate, NaCl4): TCI Chemicals, Cat.#M0483

(5) Sodium palmitate (sodium hexadecanoate, NaCl6): TCI Chemicals, Cat.#P0007

(6) Sodium stearate (sodium octadecanoate, NaCl8): TCI Chemicals, Cat.#S0081

(7) Sodium oleate (sodium trans-9-octadecanoate, NaCl8:1): TCIChemicals, Cat #O0057

(8) Pentadecylic acid (pentadecanoic acid, HCl5): TCI Chemicals, Cat#P0035

(9) Margaric acid (heptadecanoic acid, HCl7): TCI Chemicals, Cat #H0019

(10) Nonadecylic acid (nonadecanoic acid, HCl9): TCI Chemicals, Cat#N0283

(11) C1270 K ID: P&G Chemicals, Cincinnati, Ohio) prod. code 10275803

(12) C1618 K ID: P&G Chemicals, Cincinnati, Ohio) prod. code 10275805

(13) C1218 K ID: P&G Chemicals, Cincinnati, Ohio) prod. code 10275798

(14) C1214 K ID: P&G Chemicals, Cincinnati, Ohio) prod. code 10275796

(15) NaOH: 0.10 M, Fluka Chemical, Cat #319481-500ML

(16) Sodium chloride (NaCl): VWR, Cat #BDH9286-500G

(17) Lauric acid (HL): TCI Chemicals, Cat #L0011

(18) NaOH: 1.0 N, Honeywell/Fluka, Cat #35256-1L

Example 1

These include samples containing crystallizing agents with a Po value ofabout 1 and Ps value of also about 1, as determined by the BLEND TESTMETHOD, contrasting optimal and unsuitable crystallizing agents.Examples A-E (Tables 1-2) show samples prepared with different weightpercentage of sodium tetradecanoate. The increasing concentrationsincrease both firmness and temperature stability of the samples, butalso make it more difficult to express aqueous phase, as reflected inthe aqueous phase expression value. As Example E shows—at about 9 wt %,it is no longer practical to express aqueous phase, as has been observedwith soap bars that use these materials as gelling agents. Examples F-H(Table 2), show that other optimal chain length crystallizing agents,share similar trends as the previous examples. Example I-K (Table 3)have unsuitable crystallizing agents, and the sample compositions resultin liquids. Not wishing to be bound by theory, it is believed thesecrystallizing agents are either too soluble (e.g. low KrafftTemperature) or ‘kinks’ from unsaturation in the chains disruptscrystallization. Examples L-N (Table 4) demonstrate that it is possibleto create compositions with odd-chain length crystallizing agents. It isbelieved odd-chain-length crystallizing agents crystallize in adifferent manner than even chain-length crystallizing agents, so that itis surprising these compositions still form effective mesh structures.

Preparation of Compositions

Compositions were prepared using a heated mixing device. An overheadmixer (IKA Works Inc, Wilmington, N.C., model RW20 DMZ) and athree-blade impeller design was assembled. All preparations were heatedon a heating-pad assembly (VWR, Radnor, Pa., 7×7 CER Hotplate, cat. no.NO97042-690) where heating was controlled with an accompanying probe.All preparations were done in a 250 ml stainless steel beaker (ThermoFischer Scientific, Waltham, Mass.).

Examples A-K were prepared by first adding Water (1) and crystallizingagent (2-7) to the beaker. The beaker was placed on the heating-padassembly. The overhead stirrer was placed in the beaker and set torotate at 100 rpm. The heater was set at 80° C. The preparation washeated to 80° C. The solution was then divided into three 60 g plasticjars (Flak-Tech, Max 60 Cup Translucent, Cat #501 222t): one jar wasfilled to 50 ml and two jars filled to 25 ml (Examples A-H). The sampleswere cooled at room temperature 25 (±3° C.) until solid. Firmnessmeasurements were made on the 50 ml sample with the FIRMNESS TEST METHODand a thermal stability measurement was made by the THERMAL STABILITYTEST METHOD on the 50 ml sample. Water-expression measurements were madeby the AQUEOUS PHASE EXPRESSION TEST METHOD on the two 25 ml samples.Representative data demonstrates that the prototypes exhibit therequired properties for these rheological solid compositions.

Examples L-N were prepared by first adding NaOH (15) and fatty acid(8-10) to the beaker. The amount of NaOH was determined by acid number(AOCS Official Method Db 3-48—Free Acids or Free Alkali in Soap and SoapProducts). The beaker was placed on the heating-pad assembly. Theoverhead stirrer was placed in the beaker and set to rotate at 100 rpm.The heater was set at 80° C. The preparation was heated to 80° C. Thesolution was then divided into three 60 g plastic jars (Flak-Tech, Max60 Cup Translucent, Cat #501 222t): one jar was filled to 50 ml and twojars filled to 25 ml. The samples were cooled at room temperature 25(+3° C.) until solid. Firmness measurements were made on the 50 mlsample with the FIRMNESS TEST METHOD and a thermal stability measurementwas made by the THERMAL STABILITY TEST METHOD on the 50 ml sample.Water-expression measurements were made by the AQUEOUS PHASE EXPRESSIONTEST METHOD on the two 25 ml samples and blend was determined from theBLEND TEST METHOD. Representative data demonstrates that the prototypesexhibit the required properties of firmness, aqueous phase expressionand thermal stability for these rheological solid compositions.

TABLE 1 Sample A Sample B Sample C Sample D FG4005-7 FG4005-8 FG4005-9FG4005-10 Inventive Inventive Inventive Inventive (1) Water 99.501 g99.001 g 97.001 g 95.001 g (2) NaC10 — — — — (3) NaC12 — — — — (4) NaC140.500 g 1.003 g 3.001 g 5.003 g (5) NaC16 — — — — (6) NaC18 — — — — (7)NaC18:1 — — — — % Crystallizing 0.5 wt % 1.0 wt % 3.0 wt % 5.0 wt %Agent Firmness 0.51N 1.24N 8.65N 14.31N AP Expression NM7 340 J m−36,260 J m−3 7,730 J m−3 Temperature 46.7° C. 45.0° C.  48.5° C. 54.3° C.Po 1.00 1.00 1.00 1.00 Ps 1.00 1.00 1.00 1.00

TABLE 2 Sample E Sample F Sample G Sample H FG4005-12 FG4005-13FG4005-17 FG4005-23 Comparative Inventive Inventive Inventive (1) Water91.000 g 99.501 g 93.002 g 93.002 g (2) NaC10 — — — (3) NaC12 — — — —(4) NaC14 9.00 g — — — (5) NaC16 — 0.500 g 7.002 g — (6) NaC18 — — —7.000 g (7) NaC18:1 — — — — % Crystallizing 9.0 wt % 0.5 wt % 7.0 wt %7.0 wt % Agent Firmness 40.92N 0.51N 5.03N 4.19N AP Expression NM8 NM72,550 J m−3 4,230 J m−3 Temperature 56.4° C. 59.0° C. 64.3° C. 78.0° C.Po 1.00 1.00 1.00 1.00 Ps 1.00 1.00 1.00 1.00

TABLE 3 Sample I Sample J Sample K NB 1531-32 1531-33 ComparativeComparative Comparative (1) Water 48.500 g 48.611 g 48.740 g (2) NaC101.500 g — — (3) NaC12 — 1.547 g — (4) NaC14 — — — (5) NaC16 — — — (6)NaC18 — — — (7) NaC18:1 — — 1.505 g % Crystallizing 3.0 wt % 3.1 wt %3.0 wt % Agent Firmness NM1 NM1 NM1 AP Expression NM5 NM5 NM5Temperature NM3 NM3 NM3 Po 0.00 0.00 0.00 Ps [1.00] [1.00] [1.00]

TABLE 4 Sample L Sample M Sample N 1531-100 1531-101 1531-102 InventiveInventive Inventive (8) H C15 — 2.561 g — (9) H C17 2.761 g — — (10) HC19 — — 3.090 g % Crystallizing 2.76 wt % 2.56 wt % 3.09 wt % Agent (15)NaOH 97.210 g 97.442 g 96.911 g Firmness 8.10N 4.49N 4.77N AP Expression6,001 J m−3 3,688 J m−3 3,327 J m−3 Temperature 75.2° C. 63.0° C. 83.3°C. Po 1.00 1.00 1.00 Ps 1.00 1.00 1.00

Example 2

This example includes compositions that contain blends of crystallizingagent molecules, as determined by the BLEND TEST METHOD, contrasting theeffects of the relative amounts of optimal and unsuitable chain lengthcrystallizing agent molecules on the three required properties. ExamplesO-R (Table 5) show samples prepared using different weight percentagesof typical commercial fatty acid mixtures. The header shows theparticular crystallizing agent used in the preparation and the ‘fromanalysis’ shows the chain length distribution from the BLEND TESTMETHOD. All the compositions failed to crystallize and could not bemeasured for firmness, stability temperature or aqueous phaseexpression. Not wishing to be bound by theory, it is believed thesesamples have too high a level of unsuitable crystallizing agents toinitiate viable mesh formation. Examples S-V (Table 6) show the effectof adjusting the comparative levels of optimal and unsuitablecrystallizing agent chain length in the composition. While the weightpercent of the crystallizing agent remains constant in the compositions,the amount of unsuitable chain length (C10) increases, resulting in theproduction of softer compositions having lower thermal stabilitytemperature that do not crystallize to form a mesh structure. ExamplesW-Z (Table 7) show the effect of adjusting the comparative levels ofoptimal and unsuitable crystallizing agent chain length in thecomposition. While the weight percent of the crystallizing agent remainsconstant in the compositions, the amount of unsuitable chain length(C10) increases resulting in the production of softer compositions,having lower thermal stability temperature that do not crystallize toform a mesh structure. Surprisingly, the effect of the unsuitablecrystallizing agents is more detrimental in combination with the shorterchain length optimal crystallizing agent. Not wishing to be bound bytheory, but it is believed that the fibrous crystals are ‘held’ togetherprimarily by chain-to-chain interactions of the crystallizing agents inthe crystals and, being fewer with shorter chain length crystallizingagents, are more susceptible to the presence of unsuitable crystallizingagents in the crystals.

Preparation of Compositions

Compositions were prepared using a heated mixing device. An overheadmixer (IKA Works Inc, Wilmington, N.C., model RW20 DMZ) and athree-blade impeller design was assembled. All preparations were heatedon a heating-pad assembly (VWR, Radnor, Pa., 7×7 CER Hotplate, cat. no.NO97042-690) where heating was controlled with an accompanying probe.All preparations were done in a 250 ml stainless steel beaker (ThermoFischer Scientific, Waltham, Mass.).

Examples O-R were prepared by first adding NaOH (15) and commercialfatty acid (11-14) to the beaker. The amount of NaOH was determined byacid number (AOCS Official Method Db 3-48—Free Acids or Free Alkali inSoap and Soap Products). The beaker was placed on the heating-padassembly. The overhead stirrer was placed in the beaker and set torotate at 100 rpm. The heater was set at 80° C. The preparation washeated to 80° C. The solution was then divided into three 60 g plasticjars (Flak-Tech, Max 60 Cup Translucent, Cat #501 222t): one jar wasfilled to 50 ml and two jars filled to 25 ml. They were cooled at roomtemperature 25 (±3° C.). These samples remained liquid and consequentlywere not measured for firmness, thermal stability or water expression.One skilled in art recognizes that cooling compositions of crystallizingagent at different rates may result in modest differences in thefirmness, aqueous phase expression and stability temperature properties;this is common in samples prepared at different absolute weights.

Examples S-Z were prepared by first adding Water (1) and crystallizingagent (2-7) to the beaker. The beaker was placed on the heating-padassembly. The overhead stirrer was placed in the beaker and set torotate at 100 rpm. The heater was set at 80° C. The preparation washeated to 80° C. The solution was then divided into three 60 g plasticjars (Flak-Tech, Max 60 Cup Translucent, Cat #501 222t): one jar wasfilled to 50 ml and two jars filled to 25 ml (Examples A-H). The sampleswere cooled at room temperature 25 (±3° C.) until solid. Firmnessmeasurements were made on the 50 ml sample with the FIRMNESS TEST METHODand a thermal stability measurement was made by the THERMAL STABILITYTEST METHOD on the 50 ml sample. Aqueous phase expression measurementswere made by the AQUEOUS PHASE EXPRESSION TEST METHOD on the two 25 mlsamples, in all cases except Example V and Example Z, which remainedliquid. The blend was determined from the BLEND TEST METHOD.

One skilled in art recognizes that cooling compositions of crystallizingagent at different rates may result in modest differences in thefirmness, aqueous phase expression and stability temperature properties;this is common in samples prepared at different absolute weights.

TABLE 5 Sample O Sample P Sample Q Sample R 1531-119 1531-120 1531-1211531-122 (11) C-1270K (12) C-1618K (13) C-1218K (14) C-1214K ComparativeComparative Comparative Comparative Wt. Crystallizing 1.504 g 1.515 g1.509 g 1.511 g Agent (1) Water 41.607 g 43.533 g 42.195 g 41.708 g (18)NaOH 6.963 g 5.020 g 6.435 g 6.843 g % Crystallizing 3.00 wt % 3.03 wt %3.00 wt % 3.02 wt % Agent Firmness NM1 NM1 NM1 NM1 AP Expression NM5 NM5NM5 NM5 Temperature NM3 NM3 NM3 NM3 Po 0.26 0.25 0.27 0.28 Ps [0.74][0.69] [0.58] [0.72] (Chain length distribution for each crystallizingagent) HC8 — — — — HC10 — — — — HC12 1.113 g — 0.875 g 1.088 g HC13 — —— — HC14 0.391 g — 0.287 g 0.378 g HC15 — — — — HC16 — 0.300 g 0.121 g0.045 g HC17 — — — — HC18 — 0.076 g 0.226 g — HC18:1 — 1.045 g — — Other— 0.106 g — —

TABLE 6 Sample S Sample T Sample U Sample V FG4011-31 FG4011-32FG4011-33 FG4011-35 Inventive Inventive Inventive Comparative (1) Water47.501 g 47.501 g 47.500 g 47.501 g (2) NaC10 — 0.500 g 1.000 g 2.000 g(3) NaC12 — — — — (4) NaC14 2.500 g 2.000 g 1.505 g 0.501 g (5) NaC16 —— — — (6) NaC18 — — — — (7) NaC18:1 — — — — % Crystallizing 5.0 wt % 5.0wt % 5.1 wt % 5.0 wt % Agent Firmness 16.2N 13.7N 11.7N NM1 APExpression 8,107 J m−3 8,753 J m−3 2,176 J m−3 NM5 Temperature 48.6° C.44.5° C. 40.0° C. NM3 Po 1.00 0.80 0.60 0.20 Ps 1.00 0.80 0.60 [0.8]

TABLE 7 Sample W Sample X Sample Y Sample Z FG4011-43 FG4011-44FG4011-46 FG4011-78 Inventive Inventive Inventive Comparative (1) Water47.502 g 47.501 g 47.502 g 47.500 g (2) NaC10 — 0.504 g 1.500 g 2.252 g(3) NaC12 — — — — (4) NaC14 — — — — (5) NaC16 — — — — (6) NaC18 2.500 g2.002 g 1.003 g 0.253 g (7) NaC18:1 — — — — % Crystallizing 5.0 wt % 5.0wt % 5.0 wt % 5.0 wt % Agent Firmness 2.5N 1.5N 0.8N NM1 AP Expression4,560 J m−3 1,308 J m−3 TBD NM5 Temperature 73.0° C. 72.6° C. 60.6° C.NM3 Po 1.00 0.80 0.60 0.10 Ps 1.00 0.80 [0.60] [0.90]

Example 3

This include example demonstrates the effect of sodium chloride additionon the thermal stability and firmness of the rheological solidcomposition. Examples AA-AD (Table 8) show the effect of adding sodiumchloride into the hot mixture of crystallizing agent and aqueous phase.Example AA is the control, without sodium chloride addition. Example ABand Example AC have increasing amounts of sodium chloride which resultsin increasing thermal stability temperature, but with a slight decreasein firmness. Surprisingly, Example AD curds the hot mixture. Not wishingto be bound by theory, but it is believed the sodium chloride is thoughtto ‘salt out’ the crystallizing agent so that it becomes soluble only athigher temperature; and also changes the crystallization of thecrystallizing agent resulting in slightly softer compositions. However,when the sodium chloride level is too high, the solubility temperatureexceeds the processing temperature and the mixtures curd. Once curdinghas occurred, it can no longer form the crystalline mesh. Examples AE-AGdemonstrate a solution to this problem. In these examples, thecrystalline mesh is formed first and then the sodium chloride isphysically added to the top of the rheological solid composition. Inthis progression, the sodium chloride concentration increases thethermal stability temperature, while not changing the firmness. Notwishing to be bound by theory, it is believed that the crystalline meshis formed as in the control Example AA, and that the added sodiumchloride diffuses through the composition to change the solubility ofthe fibrous crystallizing agent, but not the nature of the fibers.Curding is no longer a problem, as the mixtures are crystallized firstbefore the salt addition. This approach provides a more than 20-degreeincrease in the thermal stability temperature.

Preparation of Compositions

Compositions were prepared using a heated mixing device. An overheadmixer (IKA Works Inc, Wilmington, N.C., model RW20 DMZ) and athree-blade impeller design was assembled. All preparations were heatedon a heating-pad assembly (VWR, Radnor, Pa., 7×7 CER Hotplate, cat. no.NO97042-690) where heating was controlled with an accompanying probe.All preparations were done in a 250 ml stainless steel beaker (ThermoFischer Scientific, Waltham, Mass.).

Examples AA-AD were prepared by adding Water (1), NaM (4) and sodiumchloride (16) to the beaker. The beaker was placed on the heating-padassembly. The overhead stirrer was placed in the beaker and set torotate at 100 rpm. The heater was set at 80° C. The preparation washeated to 80° C. The solution was then was poured into 60 g plastic jars(Flak-Tech, Max 60 Cup Translucent, Cat #501 222t) and allowed tocrystallize at 3° C. (±° C.) in refrigerator (VWR Refrigerator, Model#SCUCFS-0204G, or equivalent) until solid. Firmness measurements weremade with the FIRMNESS TEST METHOD, thermal stability measurement wasmade by the THERMAL STABILITY TEST METHOD and purity was determined fromthe BLEND TEST METHOD. Examples AE-AG were prepared by adding Water (1)and NaM (4) the beaker. The beaker was placed on the heating-padassembly. The overhead stirrer was placed in the beaker and set torotate at 100 rpm. The heater was set at 80° C. The preparation washeated to 80° C. The solution was then was poured into 60 g plastic jars(Flak-Tech, Max 60 Cup Translucent, Cat #501 222t) and allowed tocrystallize at 3° C. (±1° C.) in refrigerator (VWR Refrigerator, Model#SCUCFS-0204G, or equivalent) until solid. The sodium chloride (16) wasadded to the top of the composition and allowed to diffuse through thecomposition for one week, before measurement. Firmness measurements weremade with the FIRMNESS TEST METHOD, thermal stability measurement wasmade by the THERMAL STABILITY TEST METHOD and purity was determined fromthe BLEND TEST METHOD. One skilled in art recognizes that coolingcompositions of crystallizing agent at different rates may result inmodest differences in the firmness, aqueous phase expression andstability temperature properties; this is common in samples prepared atdifferent absolute weights.

TABLE 8 Sample AA Sample AB Sample AC Sample AD 1531-9 1531-10 1531-111531-12 Inventive Inventive Inventive Comparative (1) Water 48.531 g48.070 g 47.028 g 43.742 g (4) NaM 1.519 g 1.512 g 1.478 g 1.358 g %Crystallizing 3.03 wt % 3.02 wt % 2.95 wt % 2.70 wt % Agent (16) NaCl —0.508 g 1.524 g 5.087 g Wt % NaCl — 1.0 wt % 3.0 wt % 10.1 wt % Firmness6.51N 3.77N 3.15N NM2 Stability Temp 54.0° C. 61.6° C. 64.7° C. NM4 Po1.00 1.00 1.00 1.00 Ps 1.00 1.00 1.00 1.00

TABLE 9 Sample AE Sample AF Sample AG 1531-13 1531-14 1531-15 InventiveInventive Inventive Water 48.0 g 47 g 43.6 g NaM 1.5 g 1.5 g 1.35 g %Crystallizing 3.00 wt % 3.00 wt % 2.70 wt % Agent NaCl (post) 0.5 g 1.5g 5.0 g Wt % NaCl 1.0 wt % 3.0 wt % 10.1 wt % Firmness 8.47N 9.31N 9.53NStability Temp 55.5° C. 61.7° C. 76.7° C. Po 1.00 1.00 1.00 Ps 1.00 1.001.00

Example 4

This example illustrates the difference between inventive samples inthis specification relative to bar soap compositions, exemplified byExample AH. The example fails to meet all three performance criteria.Specifically, the thermal stability temperature of the composition istoo low to effectively survive reliably on the shelf life or in thesupply chain. Not wishing to be bound by theory, it is believed thechain length of 12 is far too soluble owing to the short chain length(i.e. Sample J) such that—even with a 1 wt % addition of the sodiumchloride, the C12 solubilizes below 40° C.

Preparation of Compositions

Compositions were prepared using a heated mixing device. An overheadmixer (IKA Works Inc, Wilmington, N.C., model RW20 DMZ) and athree-blade impeller design was assembled. All preparations were heatedon a heating-pad assembly (VWR, Radnor, Pa., 7×7 CER Hotplate, cat. no.NO97042-690) where heating was controlled with an accompanying probe.All preparations were done in a 250 ml stainless steel beaker (ThermoFischer Scientific, Waltham, Mass.).

A solution was prepared by adding water (1), sodium chloride (16) andlauric acid (17) to the beaker. The beaker was placed on the heatedmixing device. The overhead stirrer was placed in the beaker and set torotate at 100 rpm. The heater was set and the preparation was heated to71° C. Sodium hydroxide (15) was then added to the solution toneutralize the fatty acid and the entire mixture was heated to 95° C.The solution was then placed in cooling jars (Flak-Tech, Max 60 CupTranslucent, Cat #501 222t) and set on the bench to cool at roomtemperature 25 (+3° C.) until solid. Firmness measurements were madewith the FIRMNESS TEST METHOD, thermal stability measurement was made bythe THERMAL STABILITY TEST METHOD, water expression was made by theAQUEOUS PHASE EXPRESSION TEST METHOD and purity was determined from theBLEND TEST METHOD.

TABLE 10 Sample AH FG4007-1 Comparative (1) Water 71.500 g (16) NaCl1.002 g (17) HL  4.506 g (22.5 mmol) (15) NaOH 22.500 g (563 mmol) %Crystallizing Agent 5.0 wt % Firmness 11.43N AP Expression 2,810 J m−3Stability Temp. 35.5° C. Po 0.00 Ps [1.00]

Surface Sanitizer Treatment

Transient flora, which colonize the superficial layers of the skin, aretypically acquired by contact with other individuals and contact withcontaminated environmental surfaces while performing jobs or everydaytasks. These organisms, comprising bacteria, fungi and viruses, arecapable of surviving on skin for up to several hours, makingcontaminated hands potential vehicles for the spread of disease.

While handwashing is recognized as the standard of excellence forremoval of transient flora from the skin surface, there are manysituations where consumers and health care professionals do not haveimmediate access to running water and soap and therefore needconvenient, transportable products that provide a meaningful level ofskin antiseptic treatment. Marketed skin antiseptic compositions aregenerally limited to products in the form of a liquid gel that issqueezed or pumped out and spread over the skin, or some kind ofpre-moistened wipe or toilette that may be used to cleanse the skin,most typically on the hands but sometimes on the face or other bodyparts. These products are commonly referred to as hand sanitizers anddisinfectant wipes. Limitations of these product forms may includehaving to dispose of the plastic containers they come in, having to thedeal with the bulk of the product form, having to dispose of the usedwipe, and uncertainty of whether the product is suitable for use oncertain parts of the body. Further, few of these products are made fromnatural materials.

There is therefore a need for a new skin antiseptic composition productform that does not suffer from these limitations and that givesconsumers more flexibility in choosing a solution that meets theirneeds. In particular, there is the need for a solid product form thatcan be conveniently transported, used without generating waste, that canbe made from all natural ingredients if desired, and that can come indifferent shapes or formats that guide the consumer about its intendeduse (e.g. hands, face, for children, for adults) or that encouragebetter hygiene habits by children.

Summary

This invention highlights rheological solid skin antiseptic compositionsthat overcome the limitations of existing marketed product forms: asolid product for convenience and to enable multiple shapes and formats,and the combination of water and various actives (including naturalactives) to enable a broader selection of ingredients for the consumer.The compositions are constructed from a crystallizing agent that forms amesh. These compositions immobilize water and active in the mesh, whichare then released upon consumer use. The solid form may be adjusted tobe most suitable to specific consumers, e.g. healthcare workers,children or adults.

Materials

Skin antiseptic compositions are widely known in the art and there aremany compositions comprising a variety of materials with antimicrobialactivity. The novelty of the present invention is in the combination ofthese known efficacious materials into a unique product form thatprovides previously unavailable benefits to the consumer. Listed beloware various categories of materials that could be combined by oneskilled in the art to generate a composition that would deliver adesirable level of skin antiseptic performance and, if necessary, meetestablished guidelines for performance associated with hand sanitizersor disinfecting products for consumer skin usage.

Materials

(1) Water

(4) Sodium myristate (NaCl4)

(5) Sodium palmitate (NaCl6)

(6) Sodium stearate (NaCl8)

(19) Quaternary ammonium compounds

(20) Biguanides

(21) Iodophors

(22) Essential oils and botanical extracts

(23) Triclocarban and triclosan

In this embodiment, it is understood in the examples below, the‘crystallizing agent’ refer to group of crystallizing agents (4-6) andcombinations, thereof. In this embodiment, it is further understood inthe examples below, the ‘Quaternary ammonium compounds’ include but arenot limited to benzalkonium chloride, benzethonium chloride,cetylpyridinium chloride, cetrimonium chloride (cetyl-trimethylammoniumchloride), and cetrimonium bromide (cetyl-trimethylammonium bromide).The preferred levels are between 0.05 wt %-0.2 w %, and used at lowlevels to avoid extensive complexation with the crystallizing agents. Inthis embodiment, it is further understood in the examples below, the‘biguanides’ include, but are not limited to chlorhexidine gluconate andpolyaminopropyl biguanide. Preferred levels are between 1 wt %-4 wt %.In this embodiment, it is further understood in the examples below, the‘iodophors’ contain iodine complexed with a solubilizing agent such as asurfactant or water soluble polymer. Free iodine is slowly liberatedfrom the complex into solution. In this embodiment, it is furtherunderstood in the examples below, the ‘essential oils and botanicalextracts’ include, but are not limited to, rose oil, lavender oil,orange oil, grapefruit oil, lime oil, lemon oil, lemongrass oil, bloodorange oil, petitgrain oil, thyme oil, fennel seed oil, vanilla oil,pine oil, basil oil, cinnamon oil, rosemary oil, peppermint oil,spearmint oil, eucalyptus oil, clove oil, and cedar wood oil. These alsoinclude but are not limited to vanilla extract, lemon extract and grapefruit seed extract. The preferred levels are between 0.05 wt %-3.0 w %.In this embodiment, it is further understood in the examples below, the‘triclocarban and triclosan’ represent anti-bacterial agents. Thepreferred levels are between 0.05 wt %-1.0 w %.

Example 5

AI represents a firm composition that contains a small amount ofquaternary surfactant (19). Caution must be applied in thesecompositions as too much surfactant may degrade the crystalline mesh.AJ, AK and AL represent firm compositions that contains a small amountof biguanides, iodophors and triclocarban (TCC) and/or triclosan (TCS)respectively. AM represents a composition that includes oils. Thesecompositions may require a suspension agent to prevent separation of theoils during preparation. Further, the oils may soften the compositionsand lower the thermal stability temperature, for which sodium chlorideis introduced to the composition.

Preparation of compositions Compositions are prepared using a heatedmixing device. An overhead mixer (IKA Works Inc, Wilmington, N.C., modelRW20 DMZ) and a three-blade impeller design is assembled. Allpreparations are heated on a heating-pad assembly (VWR, Radnor, Pa., 7×7CER Hotplate, cat. no. NO97042-690) where heating was controlled with anaccompanying probe.

The solutions are prepared by adding water (1) and crystallizing agent(4-6) a stainless steel beaker (Thermo Fischer Scientific, Waltham,Mass.). The beaker is placed on the heated mixing device. The overheadstirrer is placed in the beaker and in the mixture and set to rotate at100 rpm. The mixture is heated to about 90° C., or until the mixture iscompletely clear and homogeneous. These active ingredients (19-23) areadded when the mixture is at the process temperature or at pre-cooledtemperature often about 40° C., the latter preferable for more volatileoils or oils with a low flash point. The addition of these agents oftenrequires increased stirring in rate and time, to ensure properemulsification (if necessary), and are added last to ensure the shortestpossible times at the lower temperature, preferable less that 5-10minutes.

Optionally, suspension agents may be used to prevent separation of theactive ingredients during the addition-of-active agent step. In suchcases, the x-gum (A1) and k-gum (A2) pre-mixes are added into the liquidmixture in advance of the addition of the active ingredients. Thesuspension agents are added when the temperature of the liquid mixtureis less than 60° C., and preferably less than 50° C. The suspensionagents are mixed until a homogenous composition is achieved, preferablyin less than 5-10 minutes. Once well mixed, the active ingredients areadded, as previously described.

Optionally, sodium chloride (16) is added during this stage ofprocessing, to ensure the final composition forms a viable rheologicalsolid composition. Preferred levels of the sodium chloride are between 0wt %-8 wt % and more preferably less than 5 wt %.

TABLE 11 Example AI Example AJ Example AK Example AL Inventive InventiveInventive Inventive (1) Water 100 g 100 g 100 g 100 g (4) Sodium 5.0 g5.0 g 5.0 g — myristate (NaC14) (5) Sodium — — — 4.0 g palmitate (NaC16)(6) Sodium stearate — — — 1.0 g (NaC18) (19) Quaternary 0.2 g — — —ammonium compounds (20) Biguanides — 0.2 g — — (21) Iodophors — — 0.2 g— (22) Essential oils — — — — and botanical extracts (23) Triclocarban —— — 0.5 g and triclosan

TABLE 12 Example AM Inventive (1) Water (4) Sodium myristate (NaC14) 5.0g (5) Sodium palmitate (NaC16) — (6) Sodium stearate (NaC18) — (19)Quaternary ammonium compounds — (20) Biguanides — (21) Iodophors — (22)Essential oils and botanical extracts 3.0 g (23) Triclocarban andtriclosan — (Al) X-gum stock 4.0 g (A2) K-gum stock 6.0 g (16) NaCl 2.0g

Non-Greasy Sunscreen Composition

Rheological solid compositions that deliver sunscreen from an aqueous,non-greasy chassis

Background

Sunscreens are a huge consumer market critical to the skin health ofmost people, however current products have significant consumernegatives associated with their formulations. Most current formulationsare comprised of a waxy or oily base, and delivered by a lotion, creamor spray. These composition leave a disagreeable ‘feel’ on the skin,lasting hours after the application. Further, such sunscreenformulations may damage clothes and fabrics. Such formulations arerequired by the combination of water non-soluble mineral and organiccompounds that are needed to give efficacy. Lotions, creams and spraysare also messy to apply. Consumers need a sunscreen that is water-basedto eliminate the negative qualities of a wax and oil based sunscreen,and consumers prefer the control of delivery offered by a stick product.

Summary

This invention provides water-based compositions that use a combinationof crystallizing agent to create a mesh that immobilizes the water andnon-soluble actives in a rheological solid composition. In addition toresolving the consumer negatives, these compositions are all-natural andsafe, particularly when using mineral only compositions.

Materials

(1) Water

(4-6) Crystallizing agent

(24) Mineral-base sunscreen actives

(25) Chemical-base sunscreen actives

(26) Skin feel actives

In this embodiment, it is understood in the examples below, the ‘activeagents’ includes materials 24-26. In this embodiment, it is furtherunderstood in the examples below, the ‘crystallizing agent’ includes,but not limited to, preferred agents of sodium myristate (4), sodiumpalmitate (5) and sodium stearate (6). In this embodiment, it is furtherunderstood in the examples below, the ‘mineral-base sunscreen actives’includes, but is not limited to, titanium dioxide and zinc dioxide, andcombinations thereof. Minerals are preferred to be optimal size andshape to enhance protection. In this embodiment, it is furtherunderstood in the examples below, the ‘Chemical-base sunscreen actives’includes, but are not limited to oxybenzone, avobenzone, homosalate,octinoxate, octisalate, and octocrylene, and combinations thereof. Inthis embodiment, it is further understood in the examples below, the‘skin feel actives’ includes, but are not limited to glycerin, sensate,petrolatum, mineral Oil and dimethicone and combinations thereof whichcan all be used as occlusive agents, and other materials that drivesensorial feel on the skin, to augment the efficacy of the sun screen byenhancing the water-like feel of the product. It is understood thatembodiments may include sodium chloride as needed to improve the thermalstability of the composition.

EXAMPLES

AN represents a firm product with a mineral-based composition, anall-natural and very safe composition. AO represents a firm product witha chemical-base composition, reflecting a more traditional formulation.AP represents a firm product with a mineral-based composition, with ablend of mineral-base and chemical-base actives, for high SPFformulation. AQ represents a softer product with a mineral-basedcomposition, and all-natural and very safe composition. AR represents acomposition, when a processing aid is required. In all examples, it isgenerally understood that the level of active is fixed to ensureefficacy, with a functional SPF preferably between 100 and 10 and morepreferably between 100 and 25.

Example 6

Preparation of Compositions

The preparation of rheological solid compositions in the form of asunscreen lotion stick uses the following steps:

-   1. ‘Pre-mix’ step, where crystallizing agent and water are heated to    process temperature to create a uniform liquid mixture;-   2. ‘Addition-of-actives’ step, where active ingredients and    optionally suspension agent, are incorporated into the liquid    mixture;-   3. ‘Cooling-and-molding’ step, where the liquid mixture is poured    into molds (stick container) and crystallized at a crystallization    temperature until formation of the intended rheological solid    composition.

(A1) Preparation of 1 wt % Xanthan Gum Stock (X-Gum Stock)

About 0.2 grams Euxyl PE 9010 (40), 0.3 grams SymDiol 68 (41) and 49.0grams of water are added to a Max 60 Speed Mixer cup (Flak-Tech, Max 60Cup Translucent, Cat #501 222t). Then, 0.5 grams food grade xanthan gum(38) are added to the cup. The cup is placed in the Speed Mixer(Flak-Tech) at 2700 rpm for 150 seconds. Samples are allowed to sit forabout two hours and then re-mixed at 2700 rpm for final 150 seconds.

(A2) Preparation of 1 wt % Konjac Gum Stock (K-Gum Stock)

About 0.2 grams Euxyl PE 9010 (40), 0.3 grams SymDiol 68 (41) and 49.0grams of water are added to a Max 60 Speed Mixer cup (Flak-Tech, Max 60Cup Translucent, Cat #501 222t). Then, about 0.5 grams food grade konjacgum (39) is added to the cup. The cup is placed in the Speed Mixer at2700 rpm for 150 seconds. Samples are allowed to sit for about two hoursand then re-mixed at 2700 rpm for final 150 seconds.

Preparation of Pre-Mix

Compositions are prepared using a heated mixing device. An overheadmixer (IKA Works Inc, Wilmington, N.C., model RW20 DMZ) and athree-blade impeller design is assembled. All preparations are heated ona heating-pad assembly (VWR, Radnor, Pa., 7×7 CER Hotplate, cat. no.NO97042-690) where heating may be controlled with an accompanying probe.

The solutions are prepared by adding water (1) and crystallizing agents(4-6) to the 250 ml stainless steel beaker (Thermo Fischer Scientific,Waltham, Mass.). Preferred concentrations of water are greater thanabout 80 wt % and most preferably greater than about 90 wt %. Preferredconcentrations of crystallization agent are less than about 10 wt % andpreferably less than about 5 wt %. All weight percentages are inreference to the final composition of the rheological solid composition.

The beaker is placed on the heated mixing device. The overhead stirreris placed in the beaker and set to rotate at 100 rpm. The heater is setto about 90° C. and the preparation is heated to this temperature atwhich the mixture forms a homogeneous liquid.

Addition-of-Active Agents

These active ingredients (24-26) are added when the mixture is at theprocess temperature or at pre-cooled temperature often about 40° C., thelatter is preferable for more volatile oils or oils with those having alow flash point. The addition of these agents often requires increasedstirring in rate and time, to ensure proper emulsification, and theagents are added last to ensure the shortest possible times at the lowertemperature, preferable less that 5-10 minutes. Preferred concentrationsof active ingredients are less than about 15 wt %, preferably betweenabout 1 wt %-10 wt %, all weight percent are in reference to the finalcomposition of the rheological solid composition.

Optionally, suspension agents are used to prevent separation of theactive ingredients during the addition-of-active agent step. This ismostly likely required with the addition of higher levels of activeingredients, such as between 10 wt % and 15 wt %, but may need to lowerlevels as well. In such cases, the x-gum (A1) and k-gum (A2) pre-mixesare added into the liquid mixture in advance of the addition of theactive ingredients. They are added when the temperature of the liquidmixture is less than 60° C., and preferably less than 50° C. Thesuspension agents are mixed until a homogenous composition is achieved,preferably in less than 5-10 minutes. Once well mixed, the activeingredients are added, as previously described.

Optionally, sodium chloride (16) is added during this stage ofprocessing, to ensure the final composition forms a viable rheologicalsolid composition. Preferred levels of the sodium chloride are between 0wt %-8 wt % and more preferably less than 5 wt %.

Cooling-and-Molding

The resulting mixtures are poured into a mold and cooled. Preferredshapes include a stick, beads, balls, gummy bears and other consumerpreferred shapes. The mixture is placed in these molds and the molds arekept quiescent at the crystallization temperature between 25° C. andabout 4° C., until the mixture completely crystallizes.

TABLE 13 Example AN Example AO Example AP Example AQ Inventive InventiveInventive Inventive (1) Water 89.0 g 86.0 g 87.0 g 90.0 g (4) Sodium 5.0g 5.0 g 5.0 g — myristate (NaCl4) (5) Sodium — — — 4.0 g palmitate(NaC16) (6) Sodium stearate — — — 1.0 g (NaC18) (24) Mineral-base 5.0 g— 3.5 g 5.0 g sunscreen actives (25) Chemical-base — 5.0 g 3.5 g —sunscreen actives (26) Skin feel actives 2.0 g 2.0 g 1.0 g — (16) NaCl —2.0 g 1.0 g —

TABLE 14 Example AR Inventive (1) Water 89.0 g (4) Sodium myristate(NaCl4) 5.0 g (5) Sodium palmitate (NaCl6) — (6) Sodium stearate (NaC18)— (24) Mineral-base sunscreen actives 5.0 g (25) Chemical-base sunscreenactives — (26) Skin feel actives 2.0 g (16) NaCl — (Al) X-gum stock 4.0g (A2) K-gum stock 6.0 g

Controlled Water Release from Melamine Foam Sponge

Background

There is a consumer desire for a melamine foam sponge which is‘dry-to-the-touch’ but delivers water when rubbed, squeezed or otherwiseused. In some applications, water is commonly entrained onto/intocellulose and non-woven substrates, so that the assembled product can beused to clean and treat various surfaces. The melamine foam substratesare not able to ‘hold’ the water in place in a controlled way, like mostsponges a very slight stress will express water. As a consequence, theassembled products leak, so any surfactants included in products must bedry and water must be added prior to use. Further, when using theassembled product, it is not possible to control the release of thewater so that water is often released unevenly over the length of theintend use. Finally, these assembled products are not currently able todelivering a range of non-soluble liquid actives without the use ofencapsulation due to migration of the actives. For all these reasons,consumers instead need assembled products that contain a structuredwater-rich phase that immobilizes water, water-soluble actives andwater-insoluble actives used in the aforementioned scenarios, but thatis able to release the water-rich phase under various in-use conditions.

Summary

The invention described herein is an assembled product containing amelamine foam substrate and a rheological solid composition is combinedwith the substrate to overcome the aforementioned limitations. Suchassembled products may be assembled with one or more domains of therheological solid compositions, to enhance performance. In oneembodiment, the rheological solid composition may form a layer on thesurface of the melamine foam substrate. In one embodiment, therheological solid composition may be infused within only the core of themelamine foam substrate. In another embodiment, the rheological solidcomposition may be entrained in the entirety of the substrate. Inanother embodiment, the rheological solid composition may be placedbetween two layers of substrate. In another embodiment, the rheologicalsolid composition may be placed between two different substrate layers.In another embodiment, two or more different rheological solidcompositions with different yield stress may be applied side-by-side asdifferent domains on a substrate. In another embodiment, said assembledproduct is a bathroom surface cleaner. In another embodiment, saidassembled product is a dish cleaner. In another embodiment, saidassembled product is a floor cleaner.

Materials

(1) Water

(4-6) Crystallizing agent

(27) Detersive surfactant

(28) Perfume

(29) Abrasive

(30) Melamine foam sponge

(31) Natural sponge

In this embodiment, it is understood in the examples below, the‘actives’ include, but are not limited to surfactant, perfumes andabrasive, and combinations thereof. In this embodiment, it is furtherunderstood in the examples below, the ‘detersive surfactant’ include,but are not limited to anionic, cationic, non-ionic and zwitterionicsurfactants used for cleaning such as those previously described, andcombinations thereof. In this embodiment, it is further understood inthe examples below, that the ‘perfumes’ include, but not limited to neatperfume and perfume microcapsules, and combinations thereof. It isenvisioned that the composition may include cinnamon oil, lemongrassoil, geraniol, mineral oil, and vanillin. It is envisioned that thecomposition may include mineral-based and chemical-based sun screenmaterials, for uses when the substrate is skin. In this embodiment, itis further understood in the examples below, the ‘abrasives’ include,but are not limited to small particulate added to rheological solid thataid in removing stains. In this embodiment, it is further understood inthe examples below, the ‘crystallizing agent’ includes, but is notlimited to sodium myristate, sodium palmitate and sodium stearate.

EXAMPLES

Preparation of Compositions

Compositions are prepared using a heated mixing device. An overheadmixer (IKA Works Inc, Wilmington, N.C., model RW20 DMZ) and athree-blade impeller design is assembled. All preparations are heated ona heating-pad assembly (VWR, Radnor, Pa., 7×7 CER Hotplate, cat. no.NO97042-690) where heating is controlled with an accompanying probe.

The compositions are prepared by adding water (1) and crystallizingagent (4-6) to the 250 ml stainless steel beaker (Thermo FischerScientific, Waltham, Mass.) to create a mixture. Preferredconcentrations of water are greater than about 90 wt %, more preferablygreater than about 95 wt %, most preferably greater than about 98 wt %.Preferred concentrations of crystallization agent are less than about 10wt %, more preferably less than about 5 wt %, most preferably greaterthan about 2 wt %. All weight percentages are in reference to the finalcomposition of the rheological solid composition.

The beaker is placed on the heated mixing device. The overhead stirreris placed in the beaker and in the mixture, and set to rotate at 100rpm. The mixture is heated to about 90° C. or until it forms ahomogeneous liquid mixture. Actives are dispersed in the liquid mixturebetween 90° C. and 60° C. The heated mixing device keeps the liquid atthe process temperature or cooled slightly in order to add the actives.Preferably, the temperature is kept higher than the ?? of thecrystallizing agent. However, if the temperature is lower, the active isadded and mixed within 5-10 minutes. The liquid mixture is cooledfarther such that not more than 50% is crystallized, for dosing onto thesponge substrate. Preferred concentrations of detersive surfactant areless than about 5 wt %, more preferably less than about 3 wt %, mostpreferably greater than about 2 wt %. Preferred concentrations ofperfumes are less than about 2 wt %, more preferably between about 1.5wt %, most preferably greater than about 0.5 wt %. Preferredconcentrations of abrasives are less than about 5 wt %, more preferablyless than about 3 wt %, most preferably greater than about 2 wt %. Allweight percentages are in reference to the final composition of therheological solid composition.

Example 7

An assembled product for quick cleaning a surface, where the rheologicalsolid composition contains detersive surfactant and abrasive, and formsa layer on the surface of the melamine foam substrate is created byplacing the melamine foam sponge in a solution of a liquid mixture(prior to crystallization) of rheological solid composition. The spongeis allowed to rest on the surface of the liquid mixture until therheological solid layer crystallizes. The product is used by placing theside with rheological solid composition onto the surface, and rubbingback-and-forth, at which point the water and actives are release toclean the surface.

Example 8

An assembled product for dish washing where the rheological solidcomposition contains detersive surfactant and a small level of perfumeand may be infused into the core of a melamine foam substrate created byone of two processes. In the first process, the liquid mixture ofrheological solid composition is injected into the core of the melaminefoam sponge prior to the solution crystallizing, and then the solutionis allowed to crystallize into a solid. In the second process, theliquid mixture of rheological solid composition is allowed to solidifyinto a predetermined shape and volume, the melamine sponge is thensliced/carved such that the solid can be embedded within the sponge.

Example 9

An assembled product where the rheological solid composition isentrained in the entirety of the substrate is created by submerging themelamine sponge within a rheological solid solution and allowing thesolution to fill the porous medium. The sponge is removed, withoutexuding any of the fluid, and the rheological solid composition solutionis allowed to solidify within the sponge.

Example 10

An assembled product where a rheological solid composition may be placedbetween two layers of substrate is created by allowing a rheologicalsolid solution to solidify and then sandwiching the solidifiedrheological solid composition between two melamine foam sponge segments.

Example 11

An assembled product where two or more different rheological solidcompositions with different yield stresses are applied side-by-side asdifferent domains onto a substrate is created by one of three processes.In the first process, a melamine foam sponge is partially submerged intoa rheological solid solution of a particular concentration, and thesolution is allowed to solidify. Then the virgin part of the sponge issubmerged into a rheological solid solution of a differing composition,removed and allowed to solidify. In the second process, two rheologicalsolid solutions are prepared of differing composition and independentlyallowed to form solids of a particular volume and shape. The melaminefoam sponge is then sliced/carved and one of each of the differentrheological solid compositions are embedded within the sponge. In thethird process, using a syringe the melamine foam sponge is infused witha rheological solid solution of one composition followed by an infusionof a second rheological solid solution of a different composition, andthen both solutions are allowed to crystallize.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A cleaning implement comprising: a) an erodiblefoam adapted to contact a surface to be cleaned, and b) a rheologicalsolid composition comprising: crystallizing agent and aqueous phase;wherein, the rheological solid composition has a firmness between about0.1 N to about 50.0 N as determined by the FIRMNESS TEST METHOD; athermal stability of about 40° C. to about 95° C. as determined by theTHERMAL STABILITY TEST METHOD; a liquid expression of between about 100J m-3 to about 8,000 J m-3 as determined by the AQUEOUS PHASE EXPRESSIONTEST METHOD; and wherein the crystallizing agent is a salt of fattyacids containing from about 13 to about 20 carbon atoms.
 2. The cleaningimplement of claim 1, wherein the rheological solid composition has asalt concentration greater than 1.0 wt %.
 3. The cleaning implement ofclaim 1, wherein Po is greater than about 0.3.
 4. The cleaning implementof claim 1, wherein the Po is greater than about 0.5.
 5. The cleaningimplement of claim 1, wherein Po is greater than about 0.7.
 6. Thecleaning implement of claim 1, wherein Po is greater than about 0.8. 7.The cleaning implement of claim 1, wherein Ps is greater than about 0.5.8. The cleaning implement of claim 1, wherein Ps is greater than about0.6.
 9. The cleaning implement of claim 1, wherein Ps is greater thanabout 0.7.
 10. The cleaning implement of claim 1, wherein Ps is greaterthan about 0.9.
 11. The cleaning implement of claim 1 wherein thecrystallizing agent is a metal salt.
 12. The cleaning implement of claim11 wherein the metal salt is a sodium salt.
 13. The cleaning implementof claim 12 wherein the sodium salt is at least one of sodium stearate,sodium palmitate, sodium myristate.
 14. The cleaning implement of claim13 wherein the sodium salt is at least one of sodium tridecanoate,sodium pentadecanoate, sodium heptadecanoate and sodium nanodecanoate.15. The cleaning implement of claim 1 wherein the crystallizing agent ispresent in an amount from about 0.01% to about 10% by weight of therheological solid composition.
 16. The cleaning implement of claim 1wherein the crystallizing agent is present in an amount from about 0.1%to about 7% by weight of the rheological solid composition.
 17. Thecleaning implement of claim 1 wherein the crystallizing agent is presentin an amount from about 1% to about 5% by weight of the rheologicalsolid composition.
 18. The cleaning implement of claim 1 wherein thecrystallizing agent is present in an amount from about 2% to about 4% byweight of the rheological solid composition.
 19. The cleaning implementof claim 1, wherein, the rheological solid composition, has a firmnessbetween about 0.5 N to about 25.00 N as determined by the FIRMNESS TESTMETHOD.
 20. The cleaning implement of claim 1, wherein, the rheologicalsolid composition, has a firmness between 1.0 N to about 20.0 N asdetermined by the FIRMNESS TEST METHOD.